KR102569307B1 - Fluorine Free Block Copolymer - Google Patents

Abstract

It is a fluorine-free block copolymer having at least one block segment (A), wherein the block segment (A) is a fluorine-free block having a repeating unit formed of one or two or more acrylic monomers having a long-chain hydrocarbon group having 7 to 40 carbon atoms. The copolymer imparts excellent liquid repellency to substrates such as fibers. The fluorine-free block copolymer includes (B1) a block segment having a repeating unit formed of an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms different from the segment (A), and (B2) a repeating unit formed of an acrylic monomer having no long-chain hydrocarbon group. It is preferable to have at least one segment (B) of a block segment having (B3) and a random segment formed of at least two kinds of acrylic monomers.

Description

Fluorine Free Block Copolymer

This disclosure relates to a non-fluorine block copolymer containing no fluorine atoms.

Conventionally, a fluorine-containing water and oil repellent agent comprising a fluorine compound is known. When this water and oil repellent agent is treated with a substrate such as a textile product, it exhibits good water and oil repellency.

Moreover, it is known that a fluorine-containing block polymer improves liquid repellency.

On the other hand, an acrylic block copolymer containing no fluorine has been reported. However, most of the reports are about block copolymers having blocks of hydrophilic monomers, and there is no description that block copolymers improve liquid repellency.

Patent Document 1 (Japanese Unexamined Patent Publication No. 2004-124088) discloses a hydrophilic polymer component (eg poly(ethylene oxide)) and a hydrophobic polymer component (eg poly(eg) having a mesogen side chain or a long-chain alkyl side chain). A block copolymer with methacrylate)) is disclosed.

Japanese Unexamined Patent Publication No. 2004-124088

An object of the present disclosure is to provide a block copolymer containing no fluorine atom, which imparts excellent liquid repellency.

This disclosure,

A non-fluorine block copolymer having at least one block segment (A),

The block segment (A) provides a non-fluorine block copolymer having repeating units formed from an acrylic monomer having a long-chain hydrocarbon group of 7 to 40 carbon atoms.

In addition, this disclosure,

A first-stage polymerization step of polymerizing either an acrylic monomer having a long-chain hydrocarbon group or an acrylic monomer not having a long-chain hydrocarbon group, and then a step of polymerizing the other of the acrylic monomer having a long-chain hydrocarbon group or not having a long-chain hydrocarbon group. Provided is a method for producing a fluorine-free block copolymer in which the fluorine-free block copolymer is produced by a second stage polymerization step.

In addition, this disclosure,

(1) the non-fluorine block copolymer, and

(2) A liquid medium, which is an organic solvent, or a liquid medium that is water, an organic solvent, or a mixture of water and an organic solvent.

It provides a surface treatment agent comprising a.

A preferred form of the present disclosure is as follows.

[One]

A non-fluorine block copolymer having at least one block segment (A),

The block segment (A) is a non-fluorine block copolymer having a repeating unit formed from one or two or more acrylic monomers having a long-chain hydrocarbon group of 7 to 40 carbon atoms.

[2]

The non-fluorine block copolymer has a segment (B) different from the block segment (A), and the segment (B) is

(B1) a block segment having a repeating unit formed of an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms different from the segment (A);

(B2) a block segment having a repeating unit formed of an acrylic monomer having no long-chain hydrocarbon group;

(B3) random segments formed of at least two kinds of acrylic monomers

The fluorine-free block copolymer according to [1], which has at least one of

[3]

An acrylic monomer having a long-chain hydrocarbon group has the formula:

CH ₂ =C(-R ¹² )-C(=O)-Y ¹¹ -(R ¹¹ ) _k

[Wherein, R ¹¹ is a hydrocarbon group having 7 to 40 carbon atoms,

R ¹² is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom;

Y ¹¹ is at least one selected from a 2 to 4 valent hydrocarbon group having 1 carbon atom, -C ₆ H ₄ -, -O-, -C(=O)-, -S(=O) ₂ - or -NH- It is a group consisting of (except for hydrocarbons only),

k is 1 to 3.]

The non-fluorine block copolymer according to [1] or [2], which is a monomer represented by .

[4]

In the acrylic monomer having a long chain hydrocarbon group,

Y ¹¹ is -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y' -, -Y'-R'-, -Y'-R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O) -Y'-, -Y'-R'-Y'-C(=O)-Y'- or -Y'-R'-Y'-R'-

[Wherein, Y' is each independently a direct bond, -O-, -NH- or -S(=O) ₂ -,

R' is each independently -(CH ₂ ) _m - (m is an integer of 1 to 5), a straight-chain hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -(CH ₂ ) _l -C ₆ H ₄ -(CH ₂ ) _l - (each l is independently an integer from 0 to 5, and -C ₆ H ₄ - is a phenylene group).]

Phosphorus, the fluorine-free block copolymer described in [3].

[5]

Y ¹¹ is -O-, -NH-, -OC(=O)-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O)-O- , -NH-C(=O)-NH-, -OC ₆ H ₄ -, -NH-C ₆ H ₄ -, -O-(CH ₂ ) _m -O-, -NH-(CH ₂ ) _m - NH-, -O-(CH ₂ ) _m -NH-, -NH-(CH ₂ ) _m -O-, -O-(CH ₂ ) _m -OC(=O)-, -O-(CH ₂ ) _m -C(=O)-O-, -NH-(CH ₂ ) _m -OC(=O)-, -NH-(CH ₂ ) _m -C(=O)-O-, -O-(CH ₂ ) _m -OC(=O)-NH-, -O-(CH ₂ ) _m -NH-C(=O)-O-, -O-(CH ₂ ) _m -C(=O)-NH- , -O-(CH ₂ ) _m -NH-C(=O)-, -O-(CH ₂ ) _m -NH-C(=O)-NH-, -O-(CH ₂ ) _m -OC ₆ H ₄ -, -O-(CH ₂ ) _m -NH-S(=O) ₂ -, -O-(CH ₂ ) _m -S(=O) ₂ -NH-, -NH-(CH ₂ ) _m -OC(=O)-NH-, -NH-(CH ₂ ) _m -NH-C(=O)-O-, -NH-(CH ₂ ) _m -C(=O)-NH-, -NH -(CH ₂ ) _m -NH-C(=O)-, -NH-(CH ₂ ) _m -NH-C(=O)-NH-, -NH-(CH ₂ ) _m -OC ₆ H ₄ - , -NH-(CH ₂ ) _m -NH-C ₆ H ₄ -, -NH-(CH ₂ ) _m -NH-S(=O) ₂ - or -NH-(CH ₂ ) _m -S(=O ) ₂ -NH-

[In the formula, m is an integer of 1 to 5.]

Phosphorus, the fluorine-free block copolymer described in [3].

[6]

An acrylic monomer having a long-chain hydrocarbon group,

(a1) formula:

CH ₂ =C(-R ²² )-C(=O)-Y ²¹ -R ²¹

[Wherein, R ²¹ is a hydrocarbon group having 7 to 40 carbon atoms,

R ²² is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom;

Y ²¹ is -O- or -NH-.]

A compound represented by , and

(a2) formula:

CH ₂ =C(-R ³² )-C(=O)-Y ³¹ -Z ³¹ (-Y ³² -R ³¹ ) _n

[Wherein, R ³¹ is a hydrocarbon group having 7 to 40 carbon atoms,

R ³² is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom;

Y ³¹ is -O- or -NH-;

Y ³² are each independently a group consisting of at least one selected from a direct bond, -C ₆ H ₄ -, -O-, -C(=O)-, -S(=O) ₂ -, or -NH- is,

Z ³¹ is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms;

n is 1 or 2.]

compound represented by

The non-fluorine block copolymer according to any one of [1] to [5], which is at least one type of monomer selected from the group consisting of.

[7]

In the acrylic monomer (a1),

R ²² is a hydrogen atom, a methyl group or a chlorine atom;

In the acrylic monomer (a2),

R ³² is a hydrogen atom, a methyl group or a chlorine atom;

Y ³² is a direct bond, -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O) -, -NH-S(=O) ₂ -, -S(=O) ₂ -NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C (=O)-NH-, -OC ₆ H ₄ -, -NH-C ₆ H ₄ -, -O-(CH ₂ ) _m -O-, -NH-(CH ₂ ) _m -NH-, -O -(CH ₂ ) _m -NH-, -NH-(CH ₂ ) _m -O-, -O-(CH ₂ ) _m -OC(=O)-, -O-(CH ₂ ) _m -C(= O)-O-, -NH-(CH ₂ ) _m -OC(=O)-, -NH-(CH ₂ ) _m -C(=O)-O-, -O-(CH ₂ ) _m -OC (=O)-NH-, -O-(CH ₂ ) _m -NH-C(=O)-O-, -O-(CH ₂ ) _m -C(=O)-NH-, -O-( CH ₂ ) _m -NH-C(=O)-, -O-(CH ₂ ) _m -NH-C(=O)-NH-, -O-(CH ₂ ) _m -OC ₆ H ₄ -, - NH-(CH ₂ ) _m -OC(=O)-NH-, -NH-(CH ₂ ) _m -NH-C(=O)-O-, -NH-(CH ₂ ) _m -C(=O )-NH-, -NH-(CH ₂ ) _m -NH-C(=O)-, -NH-(CH ₂ ) _m -NH-C(=O)-NH-, -NH-(CH ₂ ) _m -OC ₆ H ₄ - or -(CH ₂ ) _m -NH-C ₆ H ₄ -

[In the formula, m is an integer of 1 to 5.]

ego,

Z ³¹ is -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, a branched structure -CH ₂ CH= having a branched structure, -CH ₂ (CH-)CH ₂ - having a branched structure, -CH ₂ CH ₂ CH= having a branched structure, -CH ₂ CH ₂ CH ₂ CH ₂ CH= having a branched structure , -CH ₂ CH ₂ (CH-)CH ₂ - having a branched structure, or -CH ₂ CH ₂ CH ₂ CH= having a branched structure, the non-fluorine block copolymer described in [6].

[8]

The acrylic monomer having a long-chain hydrocarbon group WHEREIN: The non-fluorine-free block copolymer according to any one of [1] to [7], wherein the long-chain hydrocarbon group is a straight-chain or branched alkyl group having 10 to 40 carbon atoms.

[9]

The acrylic monomer having no long-chain hydrocarbon group is an acrylic monomer having a short-chain hydrocarbon group having 1 to 6 carbon atoms, an acrylic monomer having a dimethylsiloxane moiety in the side chain, an acrylic monomer having a hydrophilic group, an acrylic monomer having a cyclic hydrocarbon group, and an acrylic monomer having a crosslinking site. , or a halogenated olefin, and the hydrophilic group is an OH group, NH ₂ group, COOH group, a sulfone group or a phosphoric acid group, or an alkali metal or alkaline earth metal base of a carboxylic acid. block copolymer.

[10]

An acrylic monomer having a short-chain hydrocarbon group having 1 to 6 carbon atoms has the formula:

CH ₂ =C(-R ⁵² )-C(=O)-Y ⁵¹ -R ⁵¹

[Wherein, R ⁵¹ is a hydrocarbon group having 1 to 6 carbon atoms (which may contain oxygen atoms);

R ⁵² is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom;

Y ⁵¹ is -O- or -NH-.]

It is a compound represented by

An acrylic monomer having a hydrophilic group has the formula:

CH ₂ =C(-R ⁶² )-C(=O)-Y ⁶¹ -R ⁶¹ -(-Y ⁶² ) _q

[Wherein, R ⁶¹ is a hydrocarbon group having 1 to 6 carbon atoms or a single bond (direct bond);

R ⁶² is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom;

Y ⁶¹ is -O- or -NH-;

Y ⁶² is a hydrophilic group;

q is a number from 1 to 3.]

The non-fluorine block copolymer described in [9], which is a compound represented by

[11]

The fluorine-free block copolymer according to any one of [1] to [10], wherein the block segment (A) has a molar ratio (molar ratio of repeating units) of 30 mol% or more relative to the repeating units of the copolymer.

[12]

A first-stage polymerization step of polymerizing either an acrylic monomer having a long-chain hydrocarbon group or an acrylic monomer not having a long-chain hydrocarbon group, and then a step of polymerizing the other of the acrylic monomer having a long-chain hydrocarbon group or not having a long-chain hydrocarbon group. The method for producing a fluorine-free block copolymer according to any one of [1] to [11], wherein the fluorine-free block copolymer is produced by a second stage polymerization step.

[13]

(1) The fluorine-free block copolymer according to any one of [1] to [11], and

(2) A liquid medium, which is an organic solvent, or a liquid medium that is water, an organic solvent, or a mixture of water and an organic solvent.

A surface treatment agent comprising a.

[14]

The surface treatment agent according to [13], wherein the surface treatment agent is a water repellent agent.

[15]

The substrate to which the non-fluorine block copolymer in the surface treatment agent described in [13] or [14] has adhered.

[16]

A method for producing a treated substrate, comprising applying the surface treatment agent according to [13] or [14] to the substrate.

The block copolymer of the present disclosure is excellent in liquid repellency, that is, water repellency and oil repellency, particularly water repellency. The block copolymer has a high crystallinity and a melting point of 25°C or higher. Block copolymers have good film forming properties.

Block copolymers exhibit better performance, for example, liquid repellency, than random copolymers formed from the same monomers.

(1) non-fluorine block copolymer

The block copolymer of the present disclosure has a block segment (A) and a different segment (B). The block copolymer is a non-fluorine block copolymer having no fluorine atoms.

In this specification, a copolymer having a block segment (A) is referred to as a "block copolymer". In this specification, “fluorine-free” means “not containing a fluorine atom”.

(A) block segment

The block segment (A) has a repeating unit formed from an acrylic monomer (a) having a long-chain hydrocarbon group of 7 to 40 carbon atoms. The block segment (A) preferably contains a repeating unit formed from one type of acrylic monomer having a long-chain hydrocarbon group of 7 to 40 carbon atoms, but the block segment (A) has two types of long-chain hydrocarbon groups of 7 to 40 carbon atoms. You may have a repeating unit formed from the above (for example, 2 types or 3 types) of acrylic monomers. The block segment (A) is preferably formed from an acrylic monomer having a long chain hydrocarbon group having 7 to 40 carbon atoms. The long-chain hydrocarbon group having 7 to 40 carbon atoms is preferably a straight-chain or branched hydrocarbon group having 7 to 40 carbon atoms. The number of carbon atoms in the long-chain hydrocarbon group is preferably 10 to 40, for example 12 to 30, particularly 16 to 26. The long-chain hydrocarbon group is particularly preferably a stearyl group, an icosyl group or a behenyl group.

(a) acrylic monomer

Preferably, the acrylic monomer having a long chain hydrocarbon group has the formula:

CH ₂ =C(-R ¹² )-C(=O)-Y ¹¹ -(R ¹¹ ) _k

[Wherein, R ¹¹ is each independently a hydrocarbon group having 7 to 40 carbon atoms,

R ¹² is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom;

Y ¹¹ is a 2 to 4 valent hydrocarbon group having 1 carbon atom (particularly -CH ₂ -, -CH= and -C≡), -C ₆ H ₄ -, -O-, -C(=O)-, -S( =O) a group consisting of at least one selected from _2- or -NH- (except for divalent hydrocarbons only),

k is 1 to 3.]

It is a monomer represented by

k is 1, 2 or 3; However, in the case where Y ¹¹ has a tetravalent hydrocarbon group having 1 carbon atom, k = 3. In the case where Y ¹¹ has a trivalent hydrocarbon group having 1 carbon atom, etc., k=2. When Y ¹¹ does not have a trivalent or tetravalent hydrocarbon group having 1 carbon atom (for example, when Y ¹¹ has a divalent hydrocarbon group having 1 carbon atom (-CH ₂ -) (for example, 1 to 6)) Eh, k=1.

R ¹² may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Examples of R ¹² include a hydrogen atom, a methyl group, a chlorine atom, a bromine atom, an iodine atom and a cyano group. Since the crystallinity of the side chain is not impaired as the main chain of the obtained polymer is less rigid, R ¹² is preferably a hydrogen atom, a methyl group, or a chlorine atom, preferably a hydrogen atom or a methyl group, more preferably a hydrogen atom.

Y ¹¹ is preferably a divalent group. Examples of the 2 to 4 valent hydrocarbon group having 1 carbon atom are -CH ₂ -, -CH= having a branched structure, and -C≡ having a branched structure.

Y ¹¹ is -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y' -, -Y'-R'-, -Y'-R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O) -Y'-, -Y'-R'-Y'-C(=O)-Y'- or -Y'-R'-Y'-R'-

[Wherein, Y' is each independently a direct bond, -O-, -NH- or -S(=O) ₂ -,

R' is -(CH ₂ ) _m - (m is an integer of 1 to 5), a straight-chain hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -( CH ₂ ) _l -C ₆ H ₄ -(CH ₂ ) _l - (each l is independently an integer from 0 to 5, and -C ₆ H ₄ - is a phenylene group).]

may be

Specific examples of Y ¹¹ include -O-, -NH-, -OC(=O)-, -NH-C(=O)-, -OC(=O)-NH-, -NH-C(=O) -O-, -NH-C(=O)-NH-, -OC ₆ H ₄ -, -NH-C ₆ H ₄ -, -O-(CH ₂ ) _m -O-, -NH-(CH ₂ ) _m -NH-, -O-(CH ₂ ) _m -NH-, -NH-(CH ₂ ) _m -O-, -O-(CH ₂ ) _m -OC(=O)-, -O-( CH ₂ ) _m -C(=O)-O-, -NH-(CH ₂ ) _m -OC(=O)-, -NH-(CH ₂ ) _m -C(=O)-O-, -O -(CH ₂ ) _m -OC(=O)-NH-, -O-(CH ₂ ) _m -NH-C(=O)-O-, -O-(CH ₂ ) _m -C(=O) -NH-, -O-(CH ₂ ) _m -NH-C(=O)-, -O-(CH ₂ ) _m -NH-C(=O)-NH-, -O-(CH ₂ ) _m -OC ₆ H ₄ -, -O-(CH ₂ ) _m -NH-S(=O) ₂ -, -O-(CH ₂ ) _m -S(=O) ₂ -NH-, -NH-(CH ₂ ) _m -OC(=O)-NH-, -NH-(CH ₂ ) _m -NH-C(=O)-O-, -NH-(CH ₂ ) _m -C(=O)-NH- , -NH-(CH ₂ ) _m -NH-C(=O)-, -NH-(CH ₂ ) _m -NH-C(=O)-NH-, -NH-(CH ₂ ) _m -OC ₆ H ₄ -, -NH-(CH ₂ ) _m -NH-C ₆ H ₄ -, -NH-(CH ₂ ) _m -NH-S(=O) ₂ - or -NH-(CH ₂ ) _m -S (=0) ₂ -NH- [wherein m is an integer from 1 to 5, particularly 2 or 4].

Y ¹¹ is -O-, -NH-, -O-(CH ₂ ) _m -OC(=O)-, -O-(CH ₂ ) _m -NH-C(=O)-, -O-(CH ₂ ) _m -OC(=O)-NH-, -O-(CH ₂ ) _m -NH-C(=O)-O-, -O-(CH ₂ ) _m -NH-C(=O)- NH-, -O-(CH ₂ ) _m -NH-S(=O) ₂ - or -O-(CH ₂ ) _m -S(=O) ₂ -NH-, -NH-(CH ₂ ) _m - OC(=O)-, -NH-(CH ₂ ) _m -NH-C(=O)-, -NH-(CH ₂ ) _m -OC(=O)-NH-, -NH-(CH ₂ ) _m -NH-C(=O)-O-, -NH-(CH ₂ ) _m -NH-C(=O)-NH-, -NH-(CH ₂ ) _m -NH-S(=O) ₂ -, -NH-(CH ₂ ) _m -S(=O) ₂ -NH-

[Wherein, m is an integer from 1 to 5, particularly 2 or 4.]

It is desirable to be Y ¹¹ is -O-, -O-(CH ₂ ) _m -OC(=O)-NH-, -O-(CH ₂ ) _m -NH-C(=O)-O-, -O-(CH ₂ ) _m -NH-C(=O)-, -O-(CH ₂ ) _m -NH-S(=O) ₂ - or -O-(CH ₂ ) _m -S(=O) ₂ -NH- , more preferably -O-(CH ₂ ) _m -NH-C(=O)-.

R ¹¹ is preferably a linear or branched hydrocarbon group. The hydrocarbon group may be particularly a straight-chain hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, particularly an alkyl group. When the hydrocarbon group is short, the crystallinity of the side chains is lowered, and the water-repellent performance is also lowered. Moreover, if it is too long, since the melting point of the monomer having a corresponding hydrocarbon group becomes high, problems such as a decrease in the solubility of the monomer and instability of emulsion may occur during polymerization. In this regard, it is preferable that the hydrocarbon group has 12 to 30 carbon atoms, for example 16 to 26, particularly 18 to 22 carbon atoms.

Examples of acrylic monomers having long-chain hydrocarbon groups are

(a1) formula:

CH ₂ =C(-R ²² )-C(=O)-Y ²¹ -R ²¹

[Wherein, R ²¹ is a hydrocarbon group having 7 to 40 carbon atoms,

R ²² is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom;

Y ²¹ is -O- or -NH-.]

An acrylic monomer represented by , and

(a2) formula:

CH ₂ =C(-R ³² )-C(=O)-Y ³¹ -Z ³¹ (-Y ³² -R ³¹ ) _n

[Wherein, R ³¹ is each independently a hydrocarbon group having 7 to 40 carbon atoms;

R ³² is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom;

Y ³¹ is -O- or -NH-;

Y ³² is each independently a group composed of at least one selected from a direct bond, -O-, -C(=O)-, -S(=O) ₂ -, or -NH-;

Z ³¹ is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms;

n is 1 or 2.]

It is an acrylic monomer represented by

(a1) acrylic monomer

The acrylic monomer (a1) has the formula:

CH ₂ =C(-R ²² )-C(=O)-Y ²¹ -R ²¹

[Wherein, R ²¹ is a hydrocarbon group having 7 to 40 carbon atoms,

R ²² is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom;

Y ²¹ is -O- or -NH-.]

is a compound represented by

The acrylic monomer (a1) is a long-chain acrylate ester monomer in which Y ²¹ is -O- or a long-chain acrylamide monomer in which Y ²¹ is -NH-.

R ²¹ is preferably a linear or branched hydrocarbon group. The hydrocarbon group may be particularly a straight-chain hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, particularly an alkyl group. When the hydrocarbon group is short, the crystallinity of the side chains is lowered, and the water-repellent performance is also lowered. Moreover, if it is too long, since the melting point of the monomer having a corresponding hydrocarbon group becomes high, problems such as a decrease in the solubility of the monomer and instability of emulsion may occur during polymerization. From this point of view, those having 12 to 30, 16 to 26, and particularly 18 to 22 carbon atoms are preferred.

R ²² may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Examples of R ²² are hydrogen, methyl group, Cl, Br, I, CN. Since crystallinity of a side chain is not impaired so that the main chain of the polymer obtained is less rigid, R ²² is preferably hydrogen, a methyl group, or Cl, more preferably hydrogen or a methyl group, more preferably hydrogen.

Preferred specific examples of the long-chain acrylate ester monomer are stearyl (meth) acrylate, icosyl (meth) acrylate, behenyl (meth) acrylate, stearyl α chloroacrylate, icosyl α chloroacrylate, behenyl It is α-chloroacrylate.

Preferred specific examples of long-chain acrylamide monomers are stearyl (meth)acrylamide, icosyl (meth)acrylamide, and behenyl (meth)acrylamide.

(a2) acrylic monomer

Acrylic monomer (a2) is (meth)acrylate or (meth)acrylate having a group composed of at least one or more selected from -O-, -C(=O)-, -S(=O) ₂ - or -NH- It is acrylamide.

The acrylic monomer (a2) has the formula:

CH ₂ =C(-R ³² )-C(=O)-Y ³¹ -Z ³¹ (-Y ³² -R ³¹ ) _n

[Wherein, R ³¹ is each independently a hydrocarbon group having 7 to 40 carbon atoms;

R ³² is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom;

Y ³¹ is -O- or -NH-;

Y ³² is each independently a group composed of at least one selected from a direct bond, -O-, -C(=O)-, -S(=O) ₂ -, or -NH-;

Z ³¹ is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms;

n is 1 or 2.]

Any compound represented by

R ³¹ is preferably a linear or branched hydrocarbon group. The hydrocarbon group may be particularly a straight-chain hydrocarbon group. The hydrocarbon group is preferably an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, particularly an alkyl group. When the hydrocarbon group is short, the crystallinity of the side chains is lowered, and the water-repellent performance is also lowered. Moreover, if it is too long, since the melting point of the monomer having a corresponding hydrocarbon group becomes high, problems such as a decrease in the solubility of the monomer and instability of emulsion may occur during polymerization. From this point of view, those having 12 to 30, 16 to 26, and particularly 18 to 22 carbon atoms are preferred.

R ³² may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Examples of R ³² are hydrogen, methyl group, Cl, Br, I, CN. Since crystallinity of a side chain is not impaired so that the main chain of the polymer obtained is less rigid, R ³² is preferably hydrogen, a methyl group, or Cl, more preferably hydrogen or a methyl group, and more preferably hydrogen.

Y ³² is -Y'-, -Y'-Y'-, -Y'-C(=O)-, -C(=O)-Y'-, -Y'-C(=O)-Y' -, -Y'-R'-, -Y'-R'-Y'-, -Y'-R'-Y'-C(=O)-, -Y'-R'-C(=O) -Y'-, -Y'-R'-Y'-C(=O)-Y'- or -Y'-R'-Y'-R'-

[Wherein, Y' is each independently a direct bond, -O-, -NH- or -S(=O) ₂ -,

R' is -(CH ₂ ) _m - (m is an integer of 1 to 5), a straight-chain hydrocarbon group having an unsaturated bond of 1 to 5 carbon atoms, a hydrocarbon group having a branched structure of 1 to 5 carbon atoms, or -( CH ₂ ) _l -C ₆ H ₄ -(CH ₂ ) _l - (each l is independently an integer from 0 to 5, and -C ₆ H ₄ - is a phenylene group).]

may be

Specific examples of Y ³² include a direct bond, -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C( =O)-, -NH-S(=O) ₂ -, -S(=O) ₂ -NH-, -OC(=O)-NH-, -NH-C(=O)-O-, - NH-C(=O)-NH-, -OC ₆ H ₄ -, -NH-C ₆ H ₄ -, -O-(CH ₂ ) _m -O-, -NH-(CH ₂ ) _m -NH- , -O-(CH ₂ ) _m -NH-, -NH-(CH ₂ ) _m -O-, -O-(CH ₂ ) _m -OC(=O)-, -O-(CH ₂ ) _m - C(=O)-O-, -NH-(CH ₂ ) _m -OC(=O)-, -NH-(CH ₂ ) _m -C(=O)-O-, -O-(CH ₂ ) _m -OC(=O)-NH-, -O-(CH ₂ ) _m -NH-C(=O)-O-, -O-(CH ₂ ) _m -C(=O)-NH-, - O-(CH ₂ ) _m -NH-C(=O)-, -O-(CH ₂ ) _m -NH-C(=O)-NH-, -O-(CH ₂ ) _m -OC ₆ H ₄ -, -NH-(CH ₂ ) _m -OC(=O)-NH-, -NH-(CH ₂ ) _m -NH-C(=O)-O-, -NH-(CH ₂ ) _m -C (=O)-NH-, -NH-(CH ₂ ) _m -NH-C(=O)-, -NH-(CH ₂ ) _m -NH-C(=O)-NH-, -NH-( CH ₂ ) _m -OC ₆ H ₄ -, -NH-(CH ₂ ) _m -NH-C ₆ H ₄ -,

[In the formula, m is an integer of 1 to 5.]

am.

Y ³² is -O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, - NH-S(=O) ₂ -, -S(=O) ₂ -NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O )-NH-, -OC ₆ H ₄ - is preferred.

Z ³¹ is a direct bond or a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms, and may have a straight-chain structure or a branched structure. The number of carbon atoms in Z ³¹ is 2 to 4, preferably 2. Specific examples of Z ³¹ include a direct bond, -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH _{2 CH 2} CH ₂ -, -CH ₂ CH _{2 CH 2 CH 2} CH ₂ -, -CH ₂ CH= having a branched structure, -CH ₂ (CH-)CH ₂ -, having a branched structure -CH ₂ CH ₂ CH=, -CH ₂ CH ₂ having a branched structure CH ₂ CH ₂ CH=, -CH ₂ CH ₂ (CH-)CH ₂ - with a branched structure, -CH ₂ CH ₂ CH ₂ CH= with a branched structure.

Z ³¹ is preferably not a direct bond, and Y ³² and Z ³¹ are never a direct bond at the same time.

Acrylic monomer (a2) is CH ₂ =C(-R ³² )-C(=O)-O-(CH ₂ ) _m -NH-C(=O)-R ³¹ , CH ₂ =C(-R ³² ) -C(=O)-O-(CH ₂ ) _m -OC(=O)-NH-R ³¹ , CH ₂ =C(-R ³² )-C(=O)-O-(CH ₂ ) _m - Preferably, NH-C(=O)-OR ³¹ , CH ₂ =C(-R ³² )-C(=O)-O-(CH ₂ ) _m -NH-C(=O)-NH-R ³¹ [Here, R ³¹ and R ³² have the same meaning as above]. Acrylic monomer (a2) is particularly preferably CH ₂ =C(-R ³² )-C(=O)-O-(CH ₂ ) _m -NH-C(=O)-R ³¹ .

The acrylic monomer (a2) can be produced by reacting a hydroxyalkyl (meth)acrylate or hydroxyalkyl (meth)acrylamide with a long-chain alkyl isocyanate. Examples of the long-chain alkyl isocyanate include lauryl isocyanate, myristyl isocyanate, cetyl isocyanate, stearyl isocyanate, oleyl isocyanate, and behenyl isocyanate.

Alternatively, the acrylic monomer (a2) can also be produced by reacting a (meth)acrylate having an isocyanate group in the side chain, for example, 2-methacryloyloxyethyl methacrylate with long-chain alkylamine or long-chain alkyl alcohol. Examples of long-chain alkylamines include laurylamine, myristylamine, cetylamine, stearylamine, oleylamine, and behenylamine. Examples of the long-chain alkyl alcohol include lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, oleyl alcohol, and behenyl alcohol.

Specific examples of the acrylic monomer (a2) are as follows. The compound of the following formula is an acrylic compound in which the α-position is a hydrogen atom, but specific examples may be a methacryl compound in which the α-position is a methyl group and an α-chloroacryl compound in which the α-position is a chlorine atom.

[In the above formula, m is an integer of 1 to 5, and n is an integer of 7 to 40.]

In the acrylic monomer (a), R ³¹ is alone (for example, R ³¹ is only a compound having 17 carbon atoms), or R ³¹ is a combination of a plurality (for example, a compound having 17 carbon atoms and R ³¹ ). , a mixture of compounds having 15 carbon atoms in R ³¹ ).

Among the acrylic monomers (a2), examples of amide group-containing monomers are carboxylic acid amide alkyl (meth)acrylates.

Specific examples of the amide group-containing monomer include palmitic acid amide ethyl (meth)acrylate, stearic acid amide ethyl (meth)acrylate, behenic acid amide ethyl (meth)acrylate, myristic acid amide ethyl (meth)acrylate, Ethyl lauric acid amide (meth)acrylate, isostearic acid ethylamide (meth)acrylate, oleic acid ethylamide (meth)acrylate, tert-butylcyclohexylcaproic acid amide ethyl (meth)acrylate, adamantanecar Ethyl boxylic acid amide (meth)acrylate, naphthalenecarboxylic acid amide ethyl (meth)acrylate, anthracenecarboxylic acid amide ethyl (meth)acrylate, palmitic acid amide propyl (meth)acrylate, stearic acid amide propyl ( meth)acrylate, palmitic acid amide ethyl vinyl ether, stearic acid amide ethyl vinyl ether, palmitic acid amide ethyl aryl ether, stearic acid amide ethyl aryl ether, or mixtures thereof.

The amide group-containing monomer is preferably ethyl stearic acid amide (meth)acrylate. The amide group-containing monomer may be a mixture containing stearic acid amide ethyl (meth)acrylate. In the mixture containing ethyl stearic acid amide (meth)acrylate, the amount of ethyl stearic acid amide (meth)acrylate is preferably 55 to 99% by weight based on the total weight of the amide group-containing monomers. The remaining monomers may be, for example, palmitic acid amide ethyl (meth)acrylate.

(B) other segments

The block copolymer has, in addition to the block segment (A), another segment (B).

A block copolymer is an A-B block polymer having one block segment (A) and one other segment (B), an A-B-A block polymer having two block segments (A) and one other segment (B), or one Any B-A-B block polymer having a block segment (A) and two other segments (B) is sufficient. The block copolymer may have additional segments (C) other than the block segment (A) and other segments (B). The block copolymer may be, for example, an A-B-C block copolymer or a B-A-C block polymer.

An example of another segment (B) is

(B1) a block segment having a repeating unit formed of an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms different from the segment (A);

(B2) a block segment having a repeating unit formed of an acrylic monomer having no long-chain hydrocarbon group;

(B3) random segments formed of at least two kinds of acrylic monomers

is at least one segment of

(B1) block segment

The block segment (B1) has a repeating unit formed from an acrylic monomer having a long-chain hydrocarbon group of 7 to 40 carbon atoms and another acrylic monomer having a long-chain hydrocarbon group of 7 to 40 carbon atoms forming the segment (A). That is, the acrylic monomer having a long-chain hydrocarbon group of 7 to 40 carbon atoms forming the block segment (B1) is different from the acrylic monomer having a long-chain hydrocarbon group of 7 to 40 carbon atoms forming the block segment (A).

The preferred form of the acrylic monomer having a long-chain hydrocarbon group of 7 to 40 carbon atoms forming the block segment (B1) is the same as that of the acrylic monomer having a long-chain hydrocarbon group of 7 to 40 carbon atoms forming the block segment (A).

Examples of preferable combinations of an acrylic monomer having a long-chain hydrocarbon group of 7 to 40 carbon atoms forming the block segment (A) and an acrylic monomer having a long-chain hydrocarbon group of 7 to 40 carbon atoms forming the block segment (B1) are

CH ₂ =C(-R ¹² )-C(=O)-Y ¹¹ -(R ¹¹ ) _k

In (A), Y ¹¹ is -NH-, -O-(CH ₂ ) _m -OC(=O)-NH-, -O-(CH ₂ ) _m -NH-C(=O)-O - or -O-(CH ₂ ) _m -NH-C(=O)-, and (B1) is a monomer in which Y ¹¹ is -O- (eg, stearyl acrylate).

(B2) block segment

The block segment (B2) has repeating units formed from an acrylic monomer having no long-chain hydrocarbon group.

Examples of the acrylic monomer having no long-chain hydrocarbon group include an acrylic monomer having a short-chain hydrocarbon group of 1 to 6 carbon atoms, an acrylic monomer having a hydrophilic group, an acrylic monomer having a cyclic hydrocarbon group, and a halogenated olefin. Other examples of the acrylic monomer having no long-chain hydrocarbon group include an acrylic monomer having a dimethylsiloxane moiety in its side chain, and a divinyl compound represented by a compound having two acrylic groups.

The acrylic monomer is an acrylate ester monomer or an acrylamide monomer.

Preferred examples of acrylic monomers having a short chain hydrocarbon group of 1 to 6 carbon atoms are:

CH ₂ =C(-R ⁵² )-C(=O)-Y ⁵¹ -R ⁵¹

[Wherein, R ⁵¹ is a hydrocarbon group having 1 to 6 carbon atoms (which may contain oxygen atoms);

R ⁵² is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom;

Y ⁵¹ is -O- or -NH-.]

is a compound represented by

R ⁵¹ is a straight-chain or branched hydrocarbon group. The straight-chain or branched hydrocarbon group has 1 to 6 carbon atoms. The straight-chain or branched hydrocarbon group preferably has 1 to 4 carbon atoms, and is generally an aliphatic hydrocarbon group, particularly a saturated aliphatic hydrocarbon group, particularly preferably an alkyl group. In addition, an oxygen atom may be included. An example of a hydrocarbon group containing an oxygen atom is a glycidyl group.

R ⁵² may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Examples of R ⁵² are hydrogen, methyl group, Cl, Br, I, CN. Since the crystallinity of the side chain of the block segment (A) is not impaired as the main chain of the resulting polymer is less rigid, R ⁵² is preferably hydrogen, a methyl group, or Cl, more preferably a hydrogen or methyl group, and more preferably hydrogen do.

Particularly preferred specific examples of the short-chain acrylic monomer are methyl (meth)acrylate, methyl alpha chloroacrylate, ethyl (meth)acrylate, ethyl alpha chloroacrylate, n-butyl (meth)acrylate, t-butyl (meth) Acrylate, n-butyl α chloroacrylate, t-butyl α chloroacrylate, methyl (meth)acrylamide, n-butyl (meth)acrylamide, t-butyl (meth)acrylamide, glycidyl (meth) acrylate, glycidyl(meth)acrylamide.

Preferred examples of acrylic monomers having a hydrophilic group are:

CH ₂ =C(-R ⁶² )-C(=O)-Y ⁶¹ -(R ⁶¹ ) _p (-X ⁶¹ ) _q

[Wherein, R ⁶¹ is a hydrocarbon group having 1 to 10 carbon atoms,

R ⁶² is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom;

Y ⁶¹ is -O- or -NH-;

X ⁶¹ is a hydrophilic group,

p, 0 or 1;

q is a number from 1 to 4.]

is a compound represented by

Examples of the hydrophilic group (X ⁶¹ ) are OH groups, NH ₂ groups, COOH groups, sulfonic groups or phosphoric acid groups, alkali metal or alkaline earth metal bases of carboxylic acids. By entering a polar group such as a hydrophilic group, the liquid repellency of the copolymer that can easily form a phase-separated structure is improved. In addition, adhesion to a substrate such as cloth or glass is improved, and water-repellent performance and durability of the water-repellent performance are improved.

R ⁶¹ is a straight-chain, branched or cyclic hydrocarbon group. The number of carbon atoms in R ⁶¹ may be 1 to 6.

R ⁶² may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Examples of R ⁶² are hydrogen, methyl group, Cl, Br, I, CN,. R ⁶² is preferably hydrogen, a methyl group, or Cl, more preferably hydrogen or a methyl group, and more preferably hydrogen, since the less rigid the main chain is, the less the crystallinity of the side chain of the block segment (A) is inhibited.

Preferred specific examples of the acrylic monomer having a hydrophilic group are hydroxyethyl (meth)acrylate, hydroxyethyl (meth)acrylamide, (meth)acrylic acid, hydroxypropyl (meth)acrylate, and hydroxypropyl (meth)acrylic acid. Amide, Hydroxybutyl(meth)acrylate, Hydroxybutyl(meth)acrylamide, Carboxyethyl(meth)acrylate, Carboxyethyl(meth)acrylamide, Carboxypropyl(meth)acrylate, Carboxypropyl(meth)acryl Amide, carboxybutyl (meth)acrylate, carboxybutyl (meth)acrylamide.

Preferred examples of the cyclic hydrocarbon group-containing acrylate ester monomer are,

ceremony:

CH ₂ =C(R ⁷² )-C(=O)-Y ⁷¹ -R ⁷¹

[Wherein, R ⁷¹ is a hydrocarbon group of a cyclic hydrocarbon-containing group having 4 to 30 carbon atoms,

R ⁷² is a hydrogen atom, a monovalent organic group, or a halogen atom other than a fluorine atom;

Y ⁷¹ is -O- or -NH-.]

is a compound represented by

The cyclic hydrocarbon group-containing acrylic monomer is preferably a monomer whose glass transition point of the homopolymer does not impair the crystallinity of the block segment (A) (for example, 25°C or less).

The cyclic hydrocarbon group-containing acrylic monomer does not have a fluoroalkyl group.

R ⁷¹ is a cyclic hydrocarbon group which may have a chain group (for example, a linear or branched hydrocarbon group). As a cyclic hydrocarbon group, a saturated or unsaturated monocyclic group, polycyclic group, cross-exchange group, etc. are mentioned. It is preferable that the cyclic hydrocarbon group is saturated. The number of carbon atoms in the cyclic hydrocarbon group is 4 to 30, preferably 4 to 20. Examples of the cyclic hydrocarbon group include an aliphatic group having 4 to 30 carbon atoms, preferably 4 to 20 carbon atoms, particularly 5 to 12 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, preferably 6 to 20 carbon atoms, and preferably 7 to 30 carbon atoms. is an aromatic aliphatic hydrocarbon group of 7 to 20.

As a cyclic hydrocarbon group, a saturated or unsaturated monocyclic group, polycyclic group, cross-exchange group, etc. are mentioned. It is preferable that the cyclic hydrocarbon group is saturated.

The number of carbon atoms in the cyclic hydrocarbon group is particularly preferably 15 or less, for example 10 or less.

R ⁷² may be a hydrogen atom, a methyl group, a halogen atom other than a fluorine atom, a substituted or unsubstituted benzyl group, or a substituted or unsubstituted phenyl group. Examples of R ⁷² are hydrogen, methyl group, Cl, Br, I, CN. Since crystallinity of a side chain is not impaired so that the main chain of the polymer obtained is less rigid, R ⁷² is preferably hydrogen, a methyl group, or Cl, more preferably hydrogen or a methyl group, and more preferably hydrogen.

Specific examples of the cyclic hydrocarbon group are a cyclohexyl group, t-butylcyclohexyl group, isobornyl group, dicyclopentanyl group, dicyclopentenyl group, and adamantyl group. The acrylate group is preferably an acrylate group or a methacrylate group, but an acrylate group is particularly preferred. Specific examples of the monomer having a cyclic hydrocarbon group include cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, benzyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentanyl (meth) Acrylates, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, tricyclopentanyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adaman Tyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, etc. are mentioned.

The halogenated olefin may be a halogenated olefin having 2 to 20 carbon atoms substituted with 1 to 10 chlorine atoms, bromine atoms or iodine atoms. The halogenated olefin is preferably a chlorinated olefin having 2 to 20 carbon atoms, particularly an olefin having 2 to 5 carbon atoms having 1 to 5 chlorine atoms. Preferred specific examples of the halogenated olefin are vinyl halides, such as vinyl chloride, vinyl bromide, vinyl iodide, and vinylidene halides, such as vinylidene chloride, vinylidene bromide, and vinylidene iodide. Halogenated olefins do not have fluorine atoms.

The block segment (B2) may contain a silicon-containing monomer (silicon-containing compound). Examples of silicon-containing monomers include monomers having a dimethylsiloxane group. The monomer having a dimethylsiloxane group is preferably a compound having a dimethylsiloxane group and an olefinic carbon-carbon double bond (especially a (meth)acrylic group or a vinyl group).

Specific examples of the monomer having a dimethylsiloxane group are as follows.

CH ₂ =C(CH ₃ )CO ₂ (CH ₂ ) ₃ Si(CH ₃ ) ₂ [OSi(CH ₃ ) ₂ ] _n OSi(CH ₃ ) ₂ C ₄ H ₉ ,

CH ₂ =CHCO ₂ (CH ₂ ) ₃ Si(CH ₃ ) ₂ [OSi(CH ₃ ) ₂ ] _n OSi(CH ₃ ) ₂ C ₄ H ₉

As the length (n) of the dimethylsiloxane group is longer, the glass transition temperature of the resulting copolymer is lowered, and the flexibility, texture, and water dropability of the coating film containing the copolymer are improved. On the other hand, when n is too long, the polymerization reactivity of the monomer having a dimethylsiloxane group is lowered. 1-50 are preferable, as for the length (n) of a dimethylsiloxane group, 3-30 are more preferable, and 3-20 are more preferable.

Specific examples of the acrylic monomer having two acrylic groups and the divinyl compound include tripropylene glycol di(meth)acrylate, divinylbenzene, tetramethylene glycol di(meth)acrylate, hexamethylene glycol di(meth)acrylate ( 1,6-bisacryloylhexane), nonamethylene glycol di(meth)acrylate, decamethylene glycol di(meth)acrylate, glycerol dimethacrylate, 1-(acryloyloxy)-3-(meth)acrylate They are acryloyloxy)-2-propanol, ethylene glycol di(meth)acrylate, and 1,4-bis[4-(3-acryloyloxypropoxy)benzoyloxy-2-methylbenzene. A trivinyl compound and a tetravinyl compound may also be contained, and examples thereof include pentaerythritol tetraacrylate. When a divinyl compound (or tetravinyl or trivinyl compound) is contained, a structure containing many branched sites generally called a star is obtained. In this specification, the "block copolymer" having a block segment (A) includes one having a star structure.

(B3) random segment

The random segment (B3) is formed from at least two kinds of acrylic monomers. The acrylic monomer includes the acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms, the acrylic monomer having a short-chain hydrocarbon group having 1 to 6 carbon atoms, the acrylic monomer having the hydrophilic group, the acrylic monomer having the cyclic hydrocarbon group, the halogenated olefin, and the above. Any of monomers having a dimethylsiloxane group may be used. Other examples of acrylic monomers are divinyl compounds, silicon-containing compounds. Examples of the divinyl compound include ethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, divinylbenzene, tetramethylene glycol di(meth)acrylate, hexamethylene glycol di(meth)acrylate, and nona Methylene glycol di(meth)acrylate, decamethylene glycol di(meth)acrylate, glycerol dimethacrylate, 1-(acryloyloxy)-3-(methacryloyloxy)-2-propanol, ethylene glycol dimethacrylate, 1,4-bis[4-(3-acryloyloxypropoxy)benzoyloxy-2-methylbenzene. A trivinyl compound and a tetravinyl compound may also be contained, and an example is pentaerythritol tetraacrylate.

When it contains a divinyl compound (or a tetravinyl or trivinyl compound), it has a structure containing many branched sites generally called stars. In this specification, the "block copolymer" having a block segment (A) includes one having a star structure.

Specific examples of the combination of the two types of acrylic monomers,

stearyl (meth)acrylate/hydroxyethyl (meth)acrylate;

t-butyl (meth)acrylate/hydroxyethyl (meth)acrylate;

stearyl (meth)acrylate/hydroxybutyl (meth)acrylate;

t-butyl(meth)acrylate/hydroxybutyl(meth)acrylate,

Stearyl(meth)acrylate/t-butyl(meth)acrylate

Hydroxyethyl (meth)acrylate/hydroxybutyl methacrylate glycidyl ether,

Hydroxybutyl (meth)acrylate/hydroxybutyl methacrylate glycidyl ether,

hydroxyethyl (meth)acrylate/glycidyl (meth)acrylate,

hydroxybutyl (meth)acrylate/glycidyl (meth)acrylate;

stearyl (meth)acrylate/divinyl compound (or tetravinyl, trivinyl compound);

hydroxyethyl (meth)acrylate/divinyl compound (or tetravinyl, trivinyl compound);

hydroxybutyl (meth)acrylate/divinyl compound (or tetravinyl, trivinyl compound);

t-butyl (meth)acrylate/divinyl compound (or tetravinyl, trivinyl compound)

am.

Silicon-containing compounds can be used as monomers or chain transfer agents. One or both of a silicon-containing monomer and a silicon-containing chain transfer agent may be used.

Examples of silicon-containing monomers include monomers having a silane group. The monomer having a silane group is preferably a compound having a silane group (particularly a terminal silane group) and an olefinic carbon-carbon double bond (particularly a (meth)acrylic group or a vinyl group). The monomer which has a silane group should just be a monomer which has a terminal silane coupling group or a silane coupling group in a side chain.

The silicon-containing monomer may be a monomer having one (meth)acrylic or vinyl group and one silane group. One (meth)acrylic group or vinyl group is preferably bonded to one silane group by a (bivalent) bonding group such as a direct bond, an alkylene group having 1 to 10 carbon atoms or a siloxane group. In the case of a (meth)acrylic group, the bonding group is preferably an alkylene group having 1 to 10 carbon atoms or a siloxane group. In the case of a vinyl group, it is preferable that the bonding group is a direct bond.

Specific examples of the monomer having a silane group are as follows.

CH ₂ =CHCO ₂ (CH ₂ ) ₃ Si(OCH ₃ ) ₃ ,

CH ₂ =CHCO ₂ (CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₃ ,

CH ₂ =C(CH ₃ )CO ₂ (CH ₂ ) ₃ Si(OCH ₃ ) ₃ ,

CH ₂ =C(CH ₃ )CO ₂ (CH ₂ ) ₃ Si(OC ₂ H ₅ ) ₃ ,

CH ₂ =CHCO ₂ (CH ₂ ) ₃ SiCH ₃ (OC ₂ H ₅ ) ₂ ,

CH ₂ =C(CH ₃ )CO ₂ (CH ₂ ) ₃ SiCH ₃ (OC ₂ H ₅ ) ₂ ,

CH ₂ =C(CH ₃ )CO ₂ (CH ₂ ) ₃ SiC ₂ H ₅ (OCH ₃ ) ₂ ,

CH ₂ =CHCO ₂ (CH ₂ ) ₃ SiC ₂ H ₅ (OCH ₃ ) ₂ ,

CH ₂ =C(CH ₃ )CO ₂ (CH ₂ ) ₃ Si(CH ₃ ) ₂ (OC ₂ H ₅ ),

CH ₂ =C(CH ₃ )CO ₂ (CH ₂ ) ₃ Si(CH ₃ ) ₂ (OCH ₃ ),

CH ₂ =C(CH ₃ )CO ₂ (CH ₂ ) ₃ Si(CH ₃ ) ₂ OH;

CH ₂ =CHCO ₂ (CH ₂ ) ₃ SiCH ₃ [ON(CH ₃ )C ₂ H ₅ ] ₂ ,

CH ₂ =C(CH ₃ )CO ₂ (CH ₂ ) ₃ SiC ₆ H ₅ [ON(CH ₃ )C ₂ H ₅ ] ₂ ,

CH ₂ =C(CH ₃ )CO ₂ (CH ₂ ) ₃ Si(CH ₃ ) ₂ [OSi(CH ₃ ) ₂ ] _n OSi(CH ₃ ) ₂ C ₄ H ₉ ,

CH ₂ =CHCO ₂ (CH ₂ ) ₃ Si(CH ₃ ) ₂ [OSi(CH ₃ ) ₂ ] _n OSi(CH ₃ ) ₂ C ₄ H ₉ ,

CH ₂ =CHSi(OCH ₃ ) ₃ ,

CH ₂ =CHSi(OC ₂ H ₅ ) ₃ ,

CH ₂ =CHSiCH ₃ (OCH ₃ ) ₂ ,

CH ₂ =CHSi(CH ₃ ) ₂ (OC ₂ H ₅ ),

CH ₂ =CHSi(CH ₃ ) ₂ SiCH ₃ (OCH ₃ ) ₂ ,

CH ₂ =CHSiCH ₃ [ON(CH ₃ )C ₂ H ₅ ] ₂

vinyltrichlorosilane,

Vinyltris(2-methoxyethoxy)silane.

Silicon-containing compounds can be used as chain transfer agents. The silicon-containing chain transfer agent may be a mercapto-functional organopolysiloxane. A block copolymer having a siloxane group is obtained by polymerizing the monomers in the presence of a silicon-containing chain transfer agent. In one embodiment, the mercapto functional organopolysiloxane has siloxy units having the average formula:

(R ₂ SiO) _a (RR ^N SiO) _b (RR ^S SiO) _c

[Wherein, a is 0 to 4000, or 0 to 1000, or 0 to 400,

b is 1 to 1000, alternatively 1 to 100, alternatively 1 to 50;

c is 1 to 1000, alternatively 1 to 100, alternatively 1 to 50;

R is independently a monovalent organic group,

Alternatively, R is a hydrocarbon having 1 to 30 carbon atoms,

Alternatively, R is a monovalent alkyl group having 1 to 12 carbon atoms,

Alternatively, R is a methyl group;

R ^N is a monovalent amino functional organic group;

R ^S is a monovalent mercapto functional organic group.]

The organic functional group R ^N of the amino functional group has the formula: -R ¹ NHR ² , the formula: -R ¹ NR ₂ ² or the formula: -R ¹ NHR ¹ NHR ² (wherein each R ¹ is independently It is a divalent hydrocarbon group having 2 or more carbon atoms, and R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms.). Each R ¹ is typically an alkylene group of 2 to 20 carbon atoms.

Some examples of suitable amino functional hydrocarbon groups include:

-CH ₂ CH ₂ NH ₂ , -CH ₂ CH ₂ CH ₂ NH ₂ ,

-CH ₂ CHCH ₃ NH ₂ , -CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ ,

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ ,

-CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ NH ₂ ,

-CH ₂ CH ₂ NHCH ₃ , -CH ₂ CH ₂ CH ₂ NHCH ₃ ,

-CH ₂ (CH ₃ )CHCH ₂ NHCH ₃ , -CH ₂ CH ₂ CH ₂ CH ₂ NHCH ₃ ,

-CH ₂ CH ₂ NHCH ₂ CH ₂ NH ₂ ,

-CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ NH ₂ ,

-CH ₂ CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ CH ₂ NH ₂ ,

-CH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₃ ,

-CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ NHCH ₃ ,

-CH ₂ CH ₂ CH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ CH ₂ NHCH ₃ and

-CH ₂ CH ₂ NHCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ CH ₃ Typically the amino functional group is -CH ₂ CH ₂ CH ₂ NH ₂ .

R ^S is a formula: -R ¹ SR ² (wherein each R ¹ is independently a divalent hydrocarbon group having 2 or more carbon atoms, and R ² is hydrogen or an alkyl group having 1 to 20 carbon atoms. In the formula, each R ¹ and R ² is as described above). Each R ¹ is typically an alkylene group of 2 to 20 carbon atoms. Examples of mercapto functional groups are:

-CH ₂ CH ₂ CH ₂ SH, -CH ₂ CHCH ₃ SH, -CH ₂ CH ₂ CH ₂ CH ₂ SH, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ SH, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ SH, -CH ₂ CH ₂ SCH ₃ . Typically, the mercapto functional group is -CH ₂ CH ₂ CH ₂ SH.

In this specification, the acrylic monomer is generally (meth)acrylate or (meth)acrylamide.

In this specification, "(meth)acrylate" means acrylate or methacrylate, and "(meth)acrylamide" means acrylamide or methacrylamide.

The amount of the acrylic monomer (a) having a long-chain hydrocarbon group of 7 to 40 carbon atoms may be 30 mol% or more, preferably 35 mol% or more, based on the repeating units of the block copolymer. The amount of the monomer (a) may be 99 mol% or less with respect to the repeating unit of the block copolymer.

The molar ratio of the repeating unit in the block segment (A) and the other segment (B) is, for example, 30:70 to 99:1, preferably 35:65 to 90:10, particularly 40:60 to 90:10. It should be. When the block segment (C) is present, the amount of the repeating unit in the block segment (C) may be 0.1 to 30 mol%, for example 1 to 20 mol%, based on the repeating units of the entire block copolymer.

The number average molecular weight (Mn) of the block copolymer is generally 1000 to 1000000, for example 5000 to 500000, preferably 8000 to 200000, more preferably 8000 to 100000. The number average molecular weight (Mn) of the block copolymer is generally measured by GPC (Gel Permeation Chromatography). Copolymers synthesized by living polymerization methods such as ATRP and RAFT show a single peak, and their molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) is narrow, generally 3.0 or less, preferably 3.0 or less. At least it is less than 2.0.

Thermal properties such as melting point, glass transition temperature, crystallization temperature, and melting energy of the block copolymer of the present disclosure can be measured by differential scanning calorimetry (DSC). In general, block copolymers are known to exhibit melting points and glass transition temperatures equivalent to those of homopolymers containing only monomers as their constituent units. Even in the block copolymer of the present disclosure, it shows the same melting point as the homopolymer of the monomer of the structural unit of the block segment (A), and on the other hand, in the case of a copolymer having only a random structure without having the block segment (A), the structural unit of It shows a melting point lower than that of the homopolymer of the monomer. In the case of a polymer comprising an acrylic monomer having a long-chain hydrocarbon group, the melting point is derived from the long-chain hydrocarbon group. A higher melting point derived from a long-chain hydrocarbon group is preferable because the liquid repellency of the coating film containing the polymer is improved. Therefore, a block copolymer of the present disclosure exhibiting the same melting point as a homopolymer containing only an acrylic monomer having a long-chain hydrocarbon group is more preferable than a random copolymer.

Compared to the melting point of the homopolymer, the melting point of the block copolymer is preferably within minus 15°C (for example, 0 to 15°C lower), more preferably within minus 10°C, and particularly within minus 5°C. desirable.

For example, since the melting point (Tm) of a homopolymer using stearyl acrylate as an acrylic monomer is 50.3°C, when it has stearyl acrylate as the acrylic monomer of the block segment (A), the melting point of the block copolymer is 35.3. ° C. or higher is preferred, 40.3 ° C. or higher is more preferred, and 45.3 ° C. or higher is particularly preferred (the upper limit of the melting point of the block copolymer is the highest value of the melting point of each homopolymer of the monomers constituting the block copolymer). Similarly, since the melting point (Tm) of a homopolymer using CH ₂ =CHCO ₂ -CH ₂ CH ₂ -OC(=O)-NH-C ₁₈ H ₃₇ as an acrylic monomer is 72.3°C, CH ₂ =CHCO ₂ -CH ₂ When having CH ₂ -OC(=O)-NH-C ₁₈ H ₃₇ as the acrylic monomer of the block segment (A), the melting point of the block copolymer is preferably 57.3°C or higher, more preferably 62.3°C or higher, 67.3 degreeC or more is especially preferable. Similarly, since the melting point (Tm) of a homopolymer using CH ₂ =CHCO ₂ -CH ₂ CH ₂ -NH-C(=O)-C ₁₇ H ₃₅ as an acrylic monomer is 93.6°C, CH ₂ =CHCO ₂ -CH ₂ When having CH ₂ -NH-C(=O)-C ₁₇ H ₃₅ as the acrylic monomer of the block segment (A), the melting point of the block copolymer is preferably 78.6°C or higher, more preferably 83.6°C or higher, 88.6 degreeC or more is especially preferable. When having two or more types of acrylic monomers in the block segment, the lowest melting point is preferably within minus 15°C (0 to 15°C lower), and within minus 10°C is the lowest melting point based on the lowest melting point among the respective homopolymers. It is more preferably within minus 5°C (the upper limit of the melting point of the copolymer is the highest value of the melting point of each homopolymer of the monomers constituting the block copolymer).

From the point of view of liquid repellency, a higher melting point is preferable. However, if the melting point of the corresponding monomer is high, problems such as a decrease in the solubility of the monomer and instability of emulsion may occur during polymerization. In this regard, the melting point of the block copolymer is preferably 40°C to 200°C, more preferably 45°C to 180°C, and preferably 50°C to 170°C. The liquid-repellent performance of the copolymer can be evaluated by the difference in melting point from that of the homopolymer and the value of the melting point itself. However, even if the melting point satisfies the above temperature range, in order for the coating film containing the block polymer to exhibit good water-repellent performance, it is preferable to also satisfy the preferred conditions of the dynamic and static contact angles of water described later. Similarly, in order for a coating film containing a block polymer to exhibit good oil repellency, it is desirable to satisfy the following desirable conditions of dynamic and static contact angles of hexadecane.

The liquid repellency of the polymer can be evaluated by dissolving the block polymer in a solvent, preparing a smooth coating film by applying it to a substrate using a spin coating method or the like, and measuring the static and dynamic contact angles of the coating film. In the case of a static contact angle of water, 107° or more is preferable, 108° or more is more preferable, and 110° or more is particularly preferable. In the case of the dynamic contact angle of water, the sliding angle is preferably 20° or less, more preferably 18° or less, and particularly preferably 15° or less. In order for the polymer to exhibit water repellency, it is preferable that both the static and dynamic contact angles of water satisfy the above ranges. However, when the water sliding angle is 8° or less and exhibits very high sliding properties, it can be judged to have good water-repellent performance if the static contact angle is 103° or more. In the case of the static contact angle of hexadecane, 40° or more is preferable, and in the case of the dynamic contact angle of hexadecane, the sliding angle is preferably 9° or less, more preferably 7° or less, and particularly preferably 5° or less. In order for the polymer to exhibit oil repellency, it is preferable that the static and dynamic contact angles of hexadecane satisfy both of the above.

The water repellency of the cloth coated with the block copolymer of the present disclosure can be evaluated by a shower water repellency test (JIS-L-1092 (AATCC-22): described later). The water repellency is 0, 50, 70, 80, 90 and 100 points, in order from poor to excellent, and 70 points or more are preferable.

The strong water repellency of the fabric coated with the block copolymer of the present disclosure can be visually evaluated from the ease of splashing of water in contact with the fabric and the rate at which it flows down from the fabric when tested by the spray method of JIS-L-1092 (AATCC-22). may be Strong water repellency is 1, 2, 3, 4 and 5 points in order from poor to excellent, and 2 points or more are preferable.

A preferred mode in the shower water repellency test and strong water repellency test described above is a fabric water repellency index, and is a preferred mode of the present disclosure.

In the present disclosure, monomers are copolymerized to obtain a composition in which the copolymer is dispersed or dissolved in a medium.

(2) liquid medium

The liquid medium is at least one selected from water and organic solvents. The liquid medium may be an organic solvent alone. Alternatively, the liquid medium may be an aqueous medium. The aqueous medium may be water alone or a mixture of water and a (water-miscible) organic solvent. The amount of the water-miscible organic solvent may be 30% by weight or less, for example 10% by weight or less, based on the liquid medium.

The amount of the liquid medium may be 30 to 99.5% by weight, particularly 50 to 99.3% by weight relative to the surface treatment agent.

(3) other ingredients

The surface treatment agent may contain other components.

When the surface treatment agent is an aqueous emulsion, it is preferable to contain an emulsifier. The emulsifier may be at least one selected from nonionic emulsifiers, cationic emulsifiers, anionic emulsifiers and amphoteric emulsifiers.

nonionic surfactant

Examples of nonionic surfactants include ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides.

Examples of ethers are compounds having an oxyalkylene group (preferably a polyoxyethylene group).

An example of an ester is an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols (eg, aliphatic alcohols) having 1 to 6 valence (especially 2 to 5 valence) and 1 to 50 carbon atoms (especially 3 to 30 carbon atoms). Examples of fatty acids are saturated or unsaturated fatty acids containing 2 to 50 carbon atoms, in particular 5 to 30 carbon atoms.

An example of an ester ether is a compound obtained by adding an alkylene oxide (especially ethylene oxide) to an ester of an alcohol and a fatty acid. Examples of alcohols are alcohols (eg, aliphatic alcohols) having 1 to 6 valence (especially 2 to 5 valence) and 1 to 50 carbon atoms (especially 3 to 30 carbon atoms). Examples of fatty acids are saturated or unsaturated fatty acids containing 2 to 50 carbon atoms, in particular 5 to 30 carbon atoms.

Examples of alkanolamides are formed from fatty acids and alkanolamines. The alkanolamide may be monoalkanolamide or dialkanolamide. Examples of fatty acids are saturated or unsaturated fatty acids containing 2 to 50 carbon atoms, in particular 5 to 30 carbon atoms. The alkanolamine may be an alkanol having 2 to 50 carbon atoms, particularly 5 to 30 carbon atoms, having 1 to 3 amino groups and 1 to 5 hydroxyl groups.

The polyhydric alcohol may be a divalent to pentahydric alcohol having 10 to 30 carbon atoms.

The amine oxide may be an oxide (for example, having 5 to 50 carbon atoms) of an amine (a secondary amine or preferably a tertiary amine).

The nonionic surfactant is preferably a nonionic surfactant having an oxyalkylene group (preferably a polyoxyethylene group). It is preferable that carbon number of the alkylene group in an oxyalkylene group is 2-10. The number of oxyalkylene groups in the molecule of the nonionic surfactant is generally preferably 2 to 100.

The nonionic surfactant is preferably a nonionic surfactant selected from the group containing ethers, esters, ester ethers, alkanolamides, polyhydric alcohols and amine oxides, and having an oxyalkylene group.

Nonionic surfactants include alkylene oxide adducts of linear and/or branched aliphatic (saturated and/or unsaturated) groups, polyalkylene glycol esters of linear and/or branched fatty acids (saturated and/or unsaturated) , a polyoxyethylene (POE)/polyoxypropylene (POP) copolymer (random copolymer or block copolymer), an alkylene oxide adduct of acetylene glycol, or the like. Among these, it is preferable that the structure of the alkylene oxide addition portion and the polyalkylene glycol portion is polyoxyethylene (POE) or polyoxypropylene (POP) or a POE/POP copolymer (which may be a random copolymer or a block copolymer). .

In addition, the nonionic surfactant has a structure that does not contain an aromatic group from environmental problems (biodegradability, endocrine disruptors, etc.) is preferred.

Nonionic surfactants have the formula:

R ¹ O-(CH ₂ CH ₂ O) _p -(R ² O) _q -R ³

[Wherein, R ¹ is an alkyl group having 1 to 22 carbon atoms, an alkenyl group or an acyl group having 2 to 22 carbon atoms,

Each R ² is independently the same or different, and is an alkylene group having 3 or more carbon atoms (eg, 3 to 10);

R ³ is a hydrogen atom, an alkyl group having 1 to 22 carbon atoms or an alkenyl group having 2 to 22 carbon atoms;

p is a number greater than or equal to 2;

q is a number greater than or equal to 0 or 1.]

Any compound represented by

R ¹ preferably has 8 to 20 carbon atoms, particularly 10 to 18 carbon atoms. Preferred specific examples of R ¹ include a lauryl group, a tridecyl group, and an oleyl group.

Examples of R ² include a propylene group and a butylene group.

In the nonionic surfactant, p may be a number greater than or equal to 3 (for example, 5 to 200). q may be a number greater than or equal to 2 (for example, 5 to 200). That is, -(R ² O) _q - may form a polyoxyalkylene chain.

The nonionic surfactant may be a polyoxyethylene alkylene alkyl ether containing a hydrophilic polyoxyethylene chain and a hydrophobic oxyalkylene chain (especially polyoxyalkylene chain) in the center. Although an oxypropylene chain, an oxybutylene chain, a styrene chain, etc. are mentioned as a hydrophobic oxyalkylene chain, An oxypropylene chain is especially preferable.

Preferred nonionic surfactants have the formula:

R ¹ O-(CH ₂ CH ₂ O) _p -H

[In the formula, R ¹ and p have the same meaning as described above.]

It is a surfactant represented by

Specific examples of nonionic surfactants,

C ₁₀ H ₂₁ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₂ H ₂₅ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₆ H ₃₁ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₆ H ₃₃ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₈ H ₃₅ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₈ H ₃₇ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₂ H ₂₅ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -C ₁₂ H ₂₅

C ₁₆ H ₃₁ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -C ₁₆ H ₃₁

C ₁₆ H ₃₃ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -C ₁₂ H ₂₅

iso-C ₁₃ H ₂₇ O-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₀ H ₂₁ COO-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -H

C ₁₆ H ₃₃ COO-(CH ₂ CH ₂ O) _p -(C ₃ H ₆ O) _q -C ₁₂ H ₂₅

[In the formula, p and q have the same meaning as above.]

etc.

Specific examples of the nonionic surfactant include ethylene oxide, hexylphenol, isooctatylphenol, hexadecanol, oleic acid, alkane (C ₁₂ -C ₁₆ )thiol, sorbitan monofatty acid (C ₇ -C ₁₉ ), or alkyl Condensation products with (C ₁₂ -C ₁₈ )amines and the like are included.

The proportion of the polyoxyethylene block may be 5 to 80% by weight, for example 30 to 75% by weight, particularly 40 to 70% by weight relative to the molecular weight of the nonionic surfactant (copolymer).

The average molecular weight of the nonionic surfactant is generally 300 to 5,000, for example 500 to 3,000.

Nonionic surfactants may be used singly or in combination of two or more.

It is preferable that a nonionic surfactant is 2 or more types of combinations. In a combination of two or more, at least one nonionic surfactant is R ¹ O—(CH ₂ ) wherein the R ¹ group (and/or R ³ group) is a branched alkyl group (eg, isotridecyl group). Any compound represented by CH ₂ O) _p -(R ² O) _q -R ³ [especially R ¹ O-(CH ₂ CH ₂ O) _p -H] may be used. The amount of the nonionic surfactant in which R ¹ group is a branched alkyl group may be 5 to 100 parts by weight, for example 8 to 50 parts by weight, particularly 10 to 40 parts by weight, based on 100 parts by weight of the total nonionic surfactant (B2). . In a combination of two or more, the remaining nonionic surfactants are such that the R ¹ group (and/or R ³ group) is a (saturated and/or unsaturated) straight-chain alkyl group (eg, a lauryl group (n-lauryl group) group)), any compound represented by R ¹ O-(CH ₂ CH ₂ O) _p -(R ² O) _q -R ³ [particularly R ¹ O-(CH ₂ CH ₂ O) _p -H].

Examples of nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, and glycerin fatty acids. Esters, polyoxyethylene glycerin fatty acid esters, polyglycerin fatty acid esters, sucrose fatty acid esters, polyoxyethylene alkylamines, polyoxyethylene fatty acid amides, fatty acid alkylolamides, alkylalkanolamides, acetylene glycol, oxyethylene adducts of acetylene glycol , a polyethylene glycol polypropylene glycol block copolymer, etc. are mentioned.

Acetylene alcohol (particularly acetylene glycol) or an oxyethylene adduct of acetylene alcohol (particularly acetylene glycol) is used as the nonionic surfactant because the dynamic surface tension of the water-based emulsion is lowered (i.e., the water-based emulsion becomes easier to permeate into the substrate). desirable.

A preferred nonionic surfactant is an alcohol having an unsaturated triple bond or an alkylene oxide adduct of the alcohol (both of the alcohol and the alkylene oxide adduct are referred to as "acetylene alcohol compound"). Particularly preferred nonionic surfactants are alkylene oxide adducts of monools or polyols having unsaturated triple bonds.

An acetylene alcohol compound is a compound containing at least one triple bond and at least one hydroxyl group. The acetylene alcohol compound may be a compound containing a polyoxyalkylene moiety. Examples of the polyoxyalkylene moiety include polyoxyethylene, polyoxypropylene, random addition structures of polyoxyethylene and polyoxypropylene, and block addition structures of polyoxyethylene and polyoxypropylene.

The acetylene alcohol compound has the formula:

HO-CR ¹¹ R ¹² -C≡C-CR ¹³ R ¹⁴ -OH or

HO-CR ¹⁵ R ¹⁶ -C≡CH

[Wherein, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ are each independently the same or different, and are a hydrogen atom or an alkyl group having 1 to 30 carbon atoms.]

Any compound represented by The acetylene alcohol compound may be an alkylene oxide adduct of a compound represented by this formula. The alkyl group is preferably a straight-chain or branched alkyl group having 1 to 12 carbon atoms, and particularly preferably a straight-chain or branched alkyl group having 6 to 12 carbon atoms. For example, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, etc. are mentioned. Moreover, as an alkylene oxide, C1-C20 (especially 2-5) C1-C20 (particularly 2-5) alkylene oxide, such as ethylene oxide and a propylene oxide, and 1-50 are preferable for the number of additions of an alkylene oxide.

Specific examples of the acetylene alcohol compound include acetylene diol, propargyl alcohol, 2,5-dimethyl-3-hexyne-2,5-diol, 3,6-dimethyl-4-octyne-3,6-diol, and 2,4-diol. ,7,9-tetramethyl-5- decyn -4,7-diol, 3,5-dimethyl-1-hexyn-3-ol, 3-methyl-1-butyn-3-ol, 3-methyl-1- Pentin-3-ol, 3-hexyne-2,5-diol, 2-butyn-1,4-diol, etc. are mentioned. Polyethoxylates and ethylene oxide adducts of these embodiment compounds are also included.

A nonionic surfactant need not have a triple bond, or may have a triple bond. The nonionic surfactant may be either a nonionic surfactant having no triple bond or a nonionic surfactant having a triple bond, but a combination of a nonionic surfactant having no triple bond and a nonionic surfactant having a triple bond. do. In the combination of a nonionic surfactant having no triple bond and a nonionic surfactant having a triple bond, a nonionic surfactant having no triple bond (for example, a nonionic surfactant having an oxyalkylene group) and a triple bond The weight ratio of the nonionic surfactant (for example, acetylene alcohol compound) having a may be 10:90 to 90:10, for example, 20:80 to 80:20.

cationic surfactant

It is preferable that a cationic surfactant is a compound which does not have an amide group.

Examples of cationic surfactants include amines, amine salts, quaternary ammonium salts, imidazolines and imidazolinium salts.

The cationic surfactant is preferably an amine salt, a quaternary ammonium salt, or an oxyethylene addition-type ammonium salt. Specific examples of the cationic surfactant include, but are not particularly limited to, alkylamine salts, aminoalcohol fatty acid derivatives, polyamine fatty acid derivatives, amine salt type surfactants such as imidazoline, alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethylbenzylammonium salts, Quaternary ammonium salt type surfactants, such as a pyridinium salt, an alkyl isoquinolinium salt, and benzethonium chloride, etc. are mentioned.

Examples of cationic surfactants are

R ²¹ -N ⁺ (-R ²² )(-R ²³ )(-R ²⁴ )X ^-

[Wherein, R ²¹ , R ²² , R ²³ and R ²⁴ are each independently the same or different, and a hydrogen atom or a hydrocarbon group having 1 to 50 carbon atoms;

X is an anionic group.]

is a compound of The hydrocarbon group may have an oxygen atom, and may be, for example, oxyalkylene such as a polyoxyalkylene group (an alkylene has, for example, 2 to 5 carbon atoms). R ²¹ , R ²² , R ²³ and R ²⁴ are preferably hydrocarbon groups having 1 to 30 carbon atoms (eg, aliphatic hydrocarbons, aromatic hydrocarbons or aromatic aliphatic hydrocarbons).

Specific examples of R ²¹ , R ²² , R ²³ and R ²⁴ include an alkyl group (for example, a methyl group, a butyl group, a stearyl group, a palmityl group), an aryl group (for example, a phenyl group), an aralkyl group (for example, , benzyl group (phenylmethyl group), phenethyl group (phenylethyl group)).

Specific examples of X are halogen (eg, chlorine), acid (eg, inorganic acid such as hydrochloric acid, organic acid such as acetic acid (particularly fatty acid)).

The cationic surfactant is particularly preferably a monoalkyltrimethylammonium salt (alkyl having 4 to 30 carbon atoms.

The cationic surfactant is preferably an ammonium salt, particularly a quaternary ammonium salt. Cationic surfactants have the formula:

R ³¹ _p -N ⁺ R ³² _q X ^-

[Wherein, each R ³¹ is independently the same or different, and is a C12 or higher (eg, C ₁₂ to C ₅₀ ) linear and/or branched aliphatic (saturated and/or unsaturated) group;

R ³² Each independently the same or different, H or C1 to 4 alkyl group, benzyl group, polyoxyethylene group (the number of oxyethylene groups, for example 1 (especially 2, especially 3) to 50) (CH ₃ , C ₂ H ₅ is particularly preferred);

X is a halogen atom (eg chlorine and bromine), a C ₁ to C ₄ fatty acid base,

p is 1 or 2, q is 2 or 3, and p+q=4.]

Any ammonium salt represented by The number of carbon atoms in R ³¹ may be 12 to 50, for example 12 to 30.

Specific examples of cationic surfactants include dodecyltrimethylammonium acetate, trimethyltetradecylammonium chloride, hexadecyltrimethylammonium bromide, trimethyloctadecylammonium chloride, (dodecylmethylbenzyl)trimethylammonium chloride, benzyldodecyldimethylammonium chloride, Methyldodecyldi(hydropolyoxyethylene)ammonium chloride and benzyldodecyldi(hydropolyoxyethylene)ammonium chloride are included.

Examples of amphoteric surfactants include alanines, imidazolinium betaines, amide betaines, and betaine acetate. Specifically, lauryl betaine, stearyl betaine, and laurylcarboxymethylhydroxyethyl are Midazolium betaine, lauryl dimethylaminoacetic acid betaine, fatty acid amide propyldimethylaminoacetic acid betaine, etc. are mentioned.

The surfactant may be an amide amine surfactant which is a compound having an amide group and an amino group.

Amide amine surfactants have the formula:

R ¹¹ -C(=0)(R ¹² -)N-(CH ₂ ) _n -N-(-R ¹³ )(-R ¹⁴ )

[Wherein, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently the same or different, and a hydrogen atom or a hydrocarbon group having 1 to 30 carbon atoms;

n is 0 to 10.]

It is preferable that it is a compound represented by

R ¹¹ is preferably an alkyl group or an alkenyl group. The number of carbon atoms in R ¹¹ may be 8 to 30, for example 12 to 24. R ¹² , R ¹³ and R ¹⁴ are preferably hydrogen atoms or alkyl groups. It is preferable that R ¹² , R ¹³ and R ¹⁴ have 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms. n is 0 to 10, for example 1 to 10, in particular 2 to 5.

As specific examples of the amideamine surfactant, isostearic acid diethylaminoethylamide, oleic acid dimethylaminoethylamide, oleic acid dimethylaminopropylamide, oleic acid diethylaminoethylamide, oleic acid diethylaminopropylamide, stearic acid diethylaminoethylamide, stearic acid Diethylaminopropylamide Stearate, Dibutylaminoethyl Stearate, Dibutylaminopropyl Stearate, Dipropylaminopropyl Stearate, Dipropylaminoethyl Stearate, Dimethylaminoethyl Stearate, Dimethylaminopropyl Stearate, Palmit Acid diethylaminoethylamide, palmitic acid diethylaminopropylamide, palmitic acid dimethylaminoethylamide, palmitic acid dimethylaminopropylamide, behenic acid diethylaminoethylamide, behenic acid diethylaminopropylamide, behenic acid dimethylaminopropylamide etc. can be mentioned.

The amideamine surfactant may be nonionic or ionic (cationic), but is preferably nonionic. In the case of nonionicity, it is preferable to use an ionic compound such as an acid for ionization.

Each of a nonionic surfactant, a cationic surfactant, and an amphoteric surfactant may be 1 type or a combination of two or more.

The amount of the surfactant may be 0.1 to 20 parts by weight, for example 0.2 to 10 parts by weight, based on 100 parts by weight of the polymer.

The surface treatment agent may contain an additive as another component.

Examples of additives are silicon-containing compounds, waxes, acrylic emulsions and the like. Other examples of additives include fluoropolymers, drying rate modifiers, crosslinking agents, film formation aids, compatibilizers, surfactants, antifreezing agents, viscosity modifiers, ultraviolet absorbers, antioxidants, pH modifiers, antifoaming agents, texture modifiers, slipperiness modifiers, and antistatic agents. , hydrophilic agent, antibacterial agent, preservative, insect repellent, fragrance, flame retardant, etc.

The amount of the other components may be 0.1 to 70% by weight, for example 0.5 to 50% by weight, relative to the surface treatment agent.

[Method for producing block copolymer]

The block copolymer is preferably produced by using a living polymerization method, for example, a living radical polymerization method, a living anionic polymerization method, or a living cationic polymerization method. A living radical polymerization method is particularly preferred.

The living radical polymerization method is based on establishing a rapid equilibrium between a small amount of growing radical (free radical) species and a large amount of resting (domant) species in the growth reaction by applying heat, light, metal catalyst, etc. . Various forms of living radical polymerization with resting (domant) chains have been proposed.

For example, the ATRP method (atom transfer radical polymerization method) using an alkyl halide as a domant, the RAFT method (reversible addition fragmentation chain transfer) using a thioester, the nitroxide mediated polymerization (NMP method) using an alkoxyamine, etc. this is proposed.

The ATRP method (atom transfer radical polymerization method) is a method of polymerizing a vinyl-based monomer using a polymerization initiator having a highly reactive carbon-halogen bond and a transition metal complex serving as a polymerization catalyst (Japanese Patent Publication No. 2000-514479). Gazette et al., Sawamoto Mitsuo et al., Macromolecules 1995, 28, 1721).

The RAFT method is a method of polymerizing a vinyl monomer by adding a chain transfer agent having a high chain transfer constant called a RAFT agent to a normal radical polymerization system (M. G. Moad et al., Macromolecules 1998, 31, 5559). As the RAFT agent, thioesters can be used.

The NMP method is a method of generating stable nitroxide and polymer radicals by thermally cleavage of alkoxyamine, and polymerizing vinyl-based monomers to polymer radicals (M. K. Georges et al., Macromolecules 1993, 26, 2987). Upon cleavage, nitroxides do not initiate polymerization and react only with carbon-centered free radicals. The polymer radical reacted with the nitroxide and the monomer can be bonded again and stably exist as a domant. Living radical polymerization proceeds through the process described above.

The ATRP method (atom transfer radical polymerization method) is explained in detail below.

In the ATRP method, a vinyl monomer is polymerized using a polymerization initiator having a highly reactive carbon-halogen bond and a transition metal complex serving as a polymerization catalyst.

Examples of polymerization initiators are benzyl halides, halogenated alkanes, haloesters, haloketones, halonitrile and sulfonyl halides. Examples of the benzyl halide include 1-phenylethyl chloride or 1-bromoethylbenzene. Examples of the halogenated alkane include chloroform and carbon tetrachloride. Examples of haloesters include ethyl 2-bromoisobutyrate and ethyl 2-bromopropionate. Examples of the haloketone include bromoacetone and bromoacetophenone. As a halonitrile, 2-bromopropionitrile is mentioned. Examples of the sulfonyl halide include p-toluenesulfonyl chloride and the like.

The amount of the polymerization initiator used is not particularly limited, but is usually from 0.001 to 10 mol/liter, preferably from 0.010 to 5 mol/liter, as a concentration in the reaction system.

Although the transition metal complex is not particularly limited, it is a metal complex having a transition metal (M) selected from groups 7 to 11 of the periodic table as a central metal.

Specific examples of the transition metal (M) include, for example, Cu0, Cu ⁺ , Ni0, Ni ⁺ , Ni ²⁺ , Pd0, Pd ⁺ , Pt0, Pt ⁺ , Pt ²⁺ , Rh ⁺ , Rh ²⁺ , Rh ³⁺ , Co ⁺ , Co ²⁺ , Ir0, Ir ⁺ , Ir ²⁺ , Ir ³⁺ , Fe ^{2+ ,} Ru 2+ , Ru ³⁺ , Ru ⁴⁺ , Ru ⁵⁺ , Os ²⁺ , Os ³⁺ , Re ²⁺ , Re ³⁺ , Re ⁴⁺ , Re ⁶⁺ , Mn ²⁺ , and Mn ³⁺ . Among these, Cu+, Ni ²⁺ , Fe ²⁺ , and Ru ²⁺ are preferred from the viewpoint of catalytic activity.

The metal compound used for a transition metal complex is illustrated. Examples of copper compounds having monovalent copper metal include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, etc. Examples of nickel compounds containing divalent nickel include nickel dichloride, nickel dibromide, and diiodide Examples of the iron compound having divalent iron such as nickel include ruthenium dichloride, ruthenium dibromide, and ruthenium diiodide as the ruthenium compound having divalent ruthenium, such as iron dichloride, iron dibromide, and iron diiodide.

It is preferable to coordinate an organic ligand with respect to the transition metal (M) in terms of enabling solubilization in the polymerization solvent and reversible change of the redox conjugated complex to enhance catalytic activity. As a coordinating atom to a metal, a nitrogen atom, an oxygen atom, a phosphorus atom, a sulfur atom, etc. are mentioned, Preferably it is a nitrogen atom or a phosphorus atom. Specific examples of the organic ligands include 2,2'-bipyridyl and derivatives thereof, 1,10-phenanthroline and derivatives thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, tris(dimethylaminoethyl)amine, Triphenylphosphine, tributylphosphine, etc. are mentioned. The amount of the organic ligand used is not particularly limited, but is usually 0.1 to 100 times the amount of the transition metal (M), preferably 1 to 10 times.

The amount of the transition metal (M) used is not particularly limited, but is usually 0.01 to 100 moles, preferably 0.1 to 50 moles, and more preferably 0.1 to 10 moles, per mole of the polymerization initiating terminal of the polymerization initiator.

Atom transfer radical polymerization may coexist with a reducing agent for the transition metal. By coexisting a reducing agent, catalyst deactivation can be reduced or polymerization can proceed without strict control of deoxygenation. In addition, it becomes possible to reduce the amount of the transition metal to be used, it becomes easy to remove the transition metal from the product, and it is also superior in terms of cost. Examples of the reducing agent include zero-valent copper, ascorbic acid, sodium ascorbate, divalent tin, and sugar. It is common to add about 10 molar equivalents of the reducing agent relative to the transition metal catalyst. In addition, a radical polymerization initiator such as an azo compound may be added as a reducing agent.

Atom transfer radical polymerization can be carried out in the absence of a solvent, but can also be carried out in the presence of a solvent. As a solvent used as needed, it is water, for example; ethers such as diethyl ether, tetrahydrofuran, diphenyl ether, anisole, and dimethoxybenzene; amides such as N,N-dimethylformamide and N,N-dimethylacetamide; nitriles such as acetonitrile, propionitrile, and benzonitrile; Ester compounds or carbonate compounds, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, ethylene carbonate, and propylene carbonate; alcohols such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, t-butyl alcohol, and isoamyl alcohol; aromatic hydrocarbons such as benzene and toluene; and halogenated hydrocarbons such as chlorobenzene, methylene chloride, chloroform, chlorobenzene, and benzotrifluoride.

The amount of the solvent used is not particularly limited, but is usually 30 to 5000 parts by weight, preferably 50 to 2000 parts by weight, and more preferably 50 to 1000 parts by weight, based on 100 parts by weight of the monomer input.

Atom transfer radical polymerization is usually carried out at a temperature of -50 to 200°C, preferably 0 to 150°C, and more preferably 20 to 130°C. There is no particular restriction on the order of addition of each substance, and any method may be used. However, it is preferable to first dissolve substances other than the polymerization initiator to prepare a homogeneous solution, and then add the initiator just before raising the temperature to the polymerization temperature to perform polymerization.

After completion of the polymerization, it is industrially common to use the polymerization reaction solution as it is in the next step (for example, the step of forming the second block chain). However, you may separate the 1st block chain from a polymerization reaction liquid as needed. For example, distillation of residual monomers or solvents, re-precipitation in an appropriate solvent, filtration or centrifugation of the precipitated polymer, and washing and drying of the polymer can be performed according to well-known methods.

In addition, the transition metal complex and organic ligand used as a catalyst are diluted by diluting the polymerization solution with a good solvent for the resulting polymer, such as tetrahydrofuran (THF), toluene, etc., and passing it through a column or pad of alumina, silica, or clay. can be removed from the reaction solution. In addition, a method of treating the transition metal and organic ligands contained in the reaction solution by an extraction operation such as liquid separation or a method of treating by dispersing a metal adsorbent in the reaction solution can also be employed.

The RAFT (reversible addition cleavage chain transfer polymerization) method is described in detail below.

In the RAFT method, polymerization is advanced by allowing a dithiocarbamate derivative (manufactured by RAFT), a vinyl monomer, and a radical polymerization initiator to coexist. The resulting radical is added to the thioester compound or to the C=S bond at the end of the resulting polymer, and the original radical species is converted to the same thioester form. In this way, polymerization proceeds through an exchange chain transfer in which radical addition and cleavage to the thioester are reversibly repeated.

Any type of RAFT agent known to those skilled in the art may be used. Formula A shows the structure of a representative RAFT agent. Optimum functional groups Z and R are determined by the type of monomer to be polymerized.

Formula A

R is selected from -CH ₂ R ¹ , -CHR ¹ R' ¹ and -CR ¹ R' ¹ R" ¹ , and R ¹ , R' ¹ and R" ¹ are independently of each other optionally substituted alkyl, saturated or Unsaturated or aromatic carbocyclic or heterocyclic ring, optionally substituted alkylthio, optionally substituted alkoxy group, optionally substituted dialkylamino, organometallic group, acyl, acyloxy, carboxy (and esters thereof and/or salts), sulfonates (and salts and/or sulfonates thereof), alkoxy or aryloxycarbonyl, and polymer chains made of arbitrary polymerization mechanisms, which may be the same as or different from each other,

Z is hydrogen, halogen (chlorine, bromine, iodine), optionally substituted alkyl, optionally substituted aryl, optionally substituted heterocyclic ring, -SR ² , optionally substituted alkoxycarbonyl, optionally substituted aryloxy Carbonyl (-COOR ² ), carboxy (-COOH), optionally substituted acyloxy (-OCOR ² ), optionally substituted carbamoyl, -CONHR ² , -CONR ² R ³ , cyano (-CN) , dialkyl or diarylphosphonite [-P(=O)OR ² ₂ ], dialkyl or diarylphosphonite [-P(=O)R ² ₂ ]], polymer chain prepared by any polymerization mechanism , -OR ² group and -NR ² R ³ group, R ² and R ³ are C1 to C18 alkyl, C ₂ to C ₁₈ alkenyl, C ⁶ to C ₁₈ aryl, heterocycle, aralkyl, alkalyl selected from the group consisting of, which may be the same as or different from each other, and each of these groups may be substituted as necessary, and the substituent is epoxy, hydroxyl, alkoxy, acyl, acyloxy, carboxyl (and esters and/or salts thereof) ), sulfonates (and salts and/or sulfonates thereof), alkoxy or aryloxycarbonyls, isocyanates, cyano, silyl, helo and dialkylamino.

The amount of RAFT agent is determined by the molecular weight of the desired polymer. Since the RAFT agent binds to the end of each monomer, when a 100-mer polymer is the target, it is used around 1 mol% (0.5 to 3 mol%) with respect to 100 mol% of the monomer. In the bilaterally symmetric trithiocarbonate type RAFT agent, an A-B-A type triblock is generated, and the trithiocarbonate group derived from the RAFT agent is located not at the end but also at the center. The amount of the triblock type RAFT agent is determined in the same way as the RAFT agent described above.

The radical polymerization initiator is known to those skilled in the art, and may be any type of radical polymerization initiator selected from azo compounds, peroxide or redox type initiators. A chemical species capable of generating conventional free radicals is used as a radical polymerization initiator.

Examples of the azo compound include 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis2,4-dimethylvaleronitrile, and 2,2'-azobis(2-methylpropionamidine). dihydrochloride and 4,4'-azobis(4-cyanovaleric acid). Examples of peroxide compounds include tert-butylperoxyacetate, tert-butylperoxybenzoate (TBPO), dicumylperoxide or dibenzoyl peroxide. Examples of the redox compound include peroxosulfate salts such as potassium persulfate, sodium persulfate and ammonium persulfate, and if necessary, metabisulfite salts such as isomeric sodium bisulfite may be used together.

The polymerization initiator is generally used in an amount of 1 to 50 mol%, preferably 2 to 35 mol%, based on the weight of the RAFT agent.

The reaction of the RAFT method is determined by the radical polymerization initiator used, but is generally carried out at 40°C to 150°C in many cases. Polymerization under atmospheric pressure is mostly carried out, but polymerization under pressure is also possible.

The RAFT method can be performed in the absence of a solvent, but can also be performed in the presence of a solvent. As a solvent used as needed, it is the same as the above-mentioned ATRP method. Moreover, it is possible to react also in water, and reaction advances also in emulsion polymerization. As the emulsifier used in that case, nonionic emulsifiers, cationic emulsifiers, and anionic emulsifiers that can be used in general emulsion polymerization can be used.

Physical properties such as melting point and water repellency of the obtained block copolymer do not depend on the synthesis method. Although the ends of the obtained copolymer have a structure derived from the synthesis method (for example, thioester groups in the case of RAFT), the physical properties such as melting point and water repellency of the obtained copolymer are the same as long as they do not have specific functional groups (hydrophilic groups). do.

The obtained block copolymer can be diluted or dispersed in water or an organic solvent as needed, and then prepared in an arbitrary form such as an emulsion, an organic solvent solution, or an aerosol.

The surface treatment agent of the present disclosure may be in the form of a solution, emulsion (particularly aqueous dispersion) or aerosol. The surface treatment agent comprises a block copolymer (the active ingredient of the surface treatment agent) and a medium (particularly a liquid medium such as an organic solvent and/or water). The amount of the medium may be, for example, 5 to 99.9% by weight, particularly 10 to 80% by weight relative to the surface treatment agent.

In the surface treatment agent, the concentration of the copolymer may be 0.01 to 70% by weight, for example 0.1 to 50% by weight.

The surface treatment agent can be used as a water and oil repellent agent, an antifouling agent, a stain removal agent, a release agent, or a release agent. The surface treatment agent is particularly suitable as a water repellent.

The surface treatment agent can be applied to the object to be treated by a conventionally known method. Usually, a method of dispersing and diluting the surface treatment agent in an organic solvent or water, adhering to the surface of the object to be treated by a known method such as immersion coating, spray coating, bubble coating, and the like is employed. Moreover, if necessary, you may apply and cure with a suitable crosslinking agent (for example, block isocyanate). In addition, it is also possible to add and use an insect repellent, a softening agent, an antibacterial agent, a flame retardant, an antistatic agent, a paint fixing agent, an anti-wrinkle agent, and the like to the surface treatment agent of the present disclosure. The concentration of the copolymer in the treatment liquid brought into contact with the substrate may be 0.01 to 10% by weight (particularly in the case of dip coating), for example 0.05 to 10% by weight.

As the object to be treated with the surface treatment agent (eg, water and oil repellent) of the present disclosure, textile products, stone materials, filters (eg, electrostatic filters), dust masks, parts of fuel cells (eg, gas diffusion electrodes and gas diffusion supports), glass, paper, wood, leather, fur, asbestos, bricks, cement, metals and oxides, ceramic products, plastics, painting and plaster, and the like. As a textile product, various examples are given. For example, animal and vegetable natural fibers such as cotton, hemp, wool, and silk, synthetic fibers such as polyamide, polyester, polyvinyl alcohol, polyacrylonitrile, polyvinyl chloride, and polypropylene, and semi-synthetic fibers such as rayon and acetate. and inorganic fibers such as fibers, glass fibers, carbon fibers, and asbestos fibers, or mixed fibers thereof.

Textile products may be in the form of fibers, cloth, or the like.

The water repellent composition of the present disclosure can also be used as an antifouling agent, a release agent, and a release agent (eg, an internal release agent or an external release agent). For example, the surface of the substrate can be easily separated from other surfaces (other surfaces of the substrate or surfaces of other substrates).

The block copolymer can be applied to a fibrous substrate (eg, a fibrous product, etc.) by any of the known methods for treating a fibrous product with a liquid. When the textile product is fabric, the fabric may be immersed in the solution, or the solution may be adhered or sprayed onto the fabric. The treated textile product is dried to develop liquid repellency (water repellency and/or oil repellency), and is preferably heated at 80° C. to 200° C., for example.

Alternatively, the block copolymer may be applied to textile products by a cleaning method, and may be applied to textile products by, for example, a washing application or dry cleaning method.

The treated fibrous products are typically fabrics, including woven, knitted and nonwoven fabrics, garment-type fabrics and carpets, but may also be fibers or yarns or intermediate fiber products (eg, slivers or yarns). Textile product materials may be natural fibers (such as cotton or wool), chemical fibers (such as viscose rayon or rheocell), or synthetic fibers (such as polyester, polyamide or acrylic fibers). It may be, or it may be a mixture of fibers (for example, a mixture of natural fibers and synthetic fibers, etc.). In addition, the method of the present disclosure generally renders the textile product hydrophobic and water repellent.

Alternatively, the fibrous substrate may be leather. In order to make the leather hydrophobic and oleophobic, the preparation polymer may be applied to the leather from an aqueous solution or aqueous emulsion at various stages of leather processing, for example during the wet processing of the leather or during the finishing period of the leather.

Alternatively, the fibrous substrate may be paper. The preformed polymer may be applied to previously formed paper, or may be applied at various stages of papermaking, for example during the drying period of the paper.

"Treatment" means applying a surface treatment agent to an object to be treated by immersion, spraying, coating, or the like. By treatment, the copolymer, which is an active ingredient of the surface treatment agent, penetrates into the inside of the object to be treated and/or adheres to the surface of the object to be treated.

Example

Hereinafter, the present disclosure will be described in detail with examples, but the present disclosure is not limited to these examples.

In the following, unless otherwise specified, parts, %, or ratios represent parts by weight, % by weight, or ratio by weight.

The procedure of the test is as follows.

[Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw/Mn)]

The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw/Mn) were determined by gel permeation chromatography (GPC). For GPC, tetrahydrofuran was used as a developing solution, KF-606M, KF-601, and KF-800D manufactured by Shodex were used as columns, and molecular weight and the like were calculated in terms of polystyrene.

[Composition of Copolymer by NMR (Nuclear Magnetic Resonance)]

¹ H-NMR (nuclear magnetic resonance) measurement used heavy chloroform as a solvent.

[Measurement of thermal properties by differential scanning calorimetry (DSC)]

The melting point of the copolymer was calculated by differential scanning calorimetry (DSC). In the DSC measurement, the melting point observed in the process of cooling to -30 ° C under a nitrogen atmosphere, raising the temperature to 170 ° C at 10 ° C / min, then cooling to -30 ° C and then raising the temperature to 170 ° C at 10 ° C / min measured. In the case of a polymer having multiple melting peaks, the peak having the largest heat of fusion originating from melting of long-chain alkyl was defined as the melting point.

[Static contact angle, dynamic contact angle (slide angle) measurement]

A chloroform solution with a solid content concentration of 1.0% of the obtained copolymer was spin-coated on a silicon wafer substrate, and after annealing for 15 minutes at air-dried samples and each temperature (40 ° C, 45 ° C, 80 ° C, 120 ° C), dynamic and static Contact angles were measured, respectively. For the static contact angle, 2 µL of water or hexadecane was dropped onto the coating film, and the contact angle 1 second after deposition was measured. For the dynamic contact angle (slide angle), 20 μL of water or 5 μL of n-hexadecane was dropped on the coating film, and the substrate was tilted at a rate of 2° per second, and the angle at which the droplet began to fall was measured as the slip angle. “>85” indicates that the droplet does not fall even when the substrate is tilted by 85°. The annealing temperature "none" in Table 1 indicates that it is a measured value of the air-dried only sample.

[Water repellency test]

A treatment solution having a solid content concentration of 1.5% was prepared using chloroform as a solvent, and a cloth was immersed in the test solution, passed through a mangle, and water repellency was evaluated with a heat-treated test cloth. The water repellency of the treated cloth was evaluated according to the spray method of JIS-L-1092 (AATCC-22). It is represented by water repellency No. as shown in the table described below. The higher the score, the better the water repellency. "+" given to a number means better than that number, and "-" means worse than that number. Evaluation was performed using polyester cloth (PET) and nylon cloth (Ny).

[strong water repellency test]

When tested by the spray method of JIS-L-1092 (AATCC-22), the ease of splashing of water in contact with the cloth and the speed at which it flows down from the cloth were visually evaluated. It shows that strong water repellency is so good that a score is large.

<Example 1> Synthesis of StA/HEA by ATRP method

In a nitrogen-purged reaction vessel, 3.0 ml of toluene, 14 mg of Cu (0), 60 mg of CuBr (I), 179 mg of 2,2'-bipyridyl, 4.3 g of stearyl acrylate (StA) as a first monomer, 2-bromoy 28 µl of ethyl sobutyrate was added, and the mixture was heated and stirred at 110°C to react. After confirming the consumption of the first monomer by ¹ H NMR measurement, hydroxyethyl acrylate (HEA) was added as the second monomer. After confirming that the unreacted monomer was consumed by ¹ H NMR measurement, the polymerization solution was separated with ammonia, the Cu catalyst was removed, and reprecipitation was performed in acetone to obtain block copolymer (1). The reaction proceeded quantitatively.

<Example 2> StA/HEA

With respect to 1 mol equivalent of ethyl 2-bromoisobutyrate as an initiator, 1 mol equivalent of Cu(0), 2 mol equivalent of CuBr(I), 6 mol equivalent of 2,2'-bipyridyl, 50 mol equivalent of StA as the first monomer, second monomer A block copolymer (2) was obtained in the same manner as in Example 1, except that 50 mol equivalent of HEA was used as the reaction mixture.

<Example 3> StA/AA

The reaction was carried out in the same manner as in Example 2, except that 50 mol equivalent of StA was used as the first monomer and 50 mol equivalent of t-butylacrylate (tBuA) was used as the second monomer relative to 1 mol equivalent of ethyl 2-bromoisobutyrate as the initiator. , to obtain a block copolymer (3'). Thereafter, a deprotection reaction was performed by reacting 1 unit of tBuA with 5 equivalents of trifluoroacetic acid, and reprecipitation was performed in acetone to obtain a block copolymer (3).

<Example 4> StA/DMS

50 mol equivalent of StA as the first monomer and CH ₂ =C(CH ₃ )CO ₂ (CH ₂ ) ₃ Si(CH ₃ ) ₂ [OSi( CH ₃ ) ₂ ] _n OSi(CH ₃ ) ₂ C ₄ H ₉ (DMS) The reaction was carried out in the same manner as in Example 2 except that 4 mol equivalents were used to obtain a block copolymer (4).

<Example 5> StA/HEMA

The reaction was carried out in the same manner as in Example 2, except that 50 mol equivalent of StA was used as the first monomer and 50 mol equivalent of hydroxyl methacrylate (HEMA) was used as the second monomer, relative to 1 mol equivalent of ethyl 2-bromoisobutyrate as the initiator. , to obtain a block copolymer (5).

<Comparative Example 1> StA/HEA

With respect to 1 mol equivalent of ethyl 2-bromoisobutyrate as an initiator, 60 mol equivalent of StA as the first monomer and 40 mol equivalent of HEA as the second monomer were used, except that the first and second monomers were added to the reaction vessel at the same time. , The reaction was performed in the same manner as in Example 2 to obtain a random copolymer (1).

<Comparative Example 2> StA/AA

With respect to 1 mol equivalent of ethyl 2-bromoisobutyrate as an initiator, 50 mol equivalent of StA as the first monomer and 50 mol equivalent of tBuA as the second monomer were used, except that the first and second monomers were added to the reaction vessel at the same time , The reaction was performed in the same manner as in Example 2 to obtain a random copolymer (2'). Thereafter, a deprotection reaction was performed by reacting 1 unit of tBuA with 5 equivalents of trifluoroacetic acid, and a random copolymer (2) was obtained by re-precipitation in acetone.

<Example 6> C18URA/HEA

50 mol equivalent of CH ₂ =CHCO ₂ -CH ₂ CH ₂ -OC(=O)-NH-C ₁₈ H ₃₇ (C18URA) as the first monomer relative to 1 mol equivalent of ethyl 2-bromoisobutyrate as the initiator, and the second monomer A block copolymer (6) was obtained in the same manner as in Example 2, except that 50 mol equivalent of HEA was used as the reaction mixture.

<Example 7> C18UA/HEA

50 mol equivalent of CH ₂ =CHCO ₂ -CH ₂ CH ₂ -NH-C(=O)-OC ₁₈ H ₃₇ (C18UA) as the first monomer relative to 1 mol equivalent of ethyl 2-bromoisobutyrate as the initiator, as the second monomer A block copolymer (7) was obtained in the same manner as in Example 2, except that 50 mol equivalent of HEA was used as the mixture.

<Example 8> C18URA/tBuA

Block copolymer (8) got

<Example 9> C18URA/AA

With respect to 1 unit of tBuA of the block copolymer (8), a deprotection reaction was performed by reacting with 5 equivalents of trifluoroacetic acid, and a block copolymer (9) was obtained by re-precipitation in acetone.

<Example 10> C18URA/DMA

With respect to 1 mol equivalent of ethyl 2-bromoisobutyrate as an initiator, 40 mol equivalent of C18URA as the first monomer and CH ₂ =C(CH ₃ )CO ₂ (CH ₂ ) ₃ Si(CH ₃ ) ₂ [OSi( CH ₃ ) ₂ ] _n OSi(CH ₃ ) ₂ C ₄ H ₉ (DMS) The reaction was carried out in the same manner as in Example 2 except that 4 mol equivalents were used to obtain block copolymer (10).

<Example 11> Synthesis of C18URA/StA by RAFT method

In a reaction vessel purged with nitrogen, 35 mg of cyanomethyldodecyltrithiocarbonate as a RAFT initiator, 2,2'-azobisisobutyronitrile (AIBN) and C18URA as a first monomer were added in an equivalent amount of 0.1 mol each to the RAFT initiator, 65 mol equivalents and 3.0 ml of toluene were added, and the mixture was heated and stirred at 70°C to react. After confirming the consumption of the first monomer by ¹ H NMR measurement, 35 mol equivalents of StA (relative to the RAFT initiator) were added as the second monomer. After confirming that unreacted monomers were consumed by ¹ H NMR measurement, block copolymer (11) was obtained by re-precipitation in acetone. The reaction proceeded quantitatively.

<Example 12> C18URA/StA

A block copolymer (12 ) was obtained.

<Comparative Example 3> C18URA/HEA

With respect to 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate, 50 mol equivalent of C18URA as the first monomer and 50 mol equivalent of HEA as the second monomer were used, except that the first and second monomers were added to the reaction vessel at the same time. was reacted in the same manner as in Example 11 to obtain a random copolymer (3).

<Comparative Example 4> C18URA/tBuA

With respect to 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate, 50 mol equivalent of C18URA as the first monomer and 50 mol equivalent of tBuA as the second monomer were used, except that the first and second monomers were added to the reaction vessel at the same time. was reacted in the same manner as in Example 11 to obtain a random copolymer (4).

<Comparative Example 5> C18URA/AA

A deprotection reaction was performed by reacting 1 unit of tBuA of the random copolymer (4) with 5 equivalents of trifluoroacetic acid, followed by reprecipitation in acetone to obtain a random copolymer (5).

<Comparative Example 6> C18URA/StA

With respect to 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate, 50 mol equivalent of C18URA as the first monomer and 50 mol equivalent of StA as the second monomer were used, except that the first and second monomers were added to the reaction vessel at the same time. was reacted in the same manner as in Example 11 to obtain a random copolymer (6).

<Example 13> C18URA/HEA/StA

In a nitrogen-purged reaction vessel, 35 mg of RAFT initiator cyanomethyldodecyltrithiocarbonate, 2,2'-azobisisobutyronitrile (AIBN) and C18URA as a first monomer were added in an equivalent amount of 0.1 mol, 30 mol, respectively, relative to the RAFT initiator. The equivalent amount and 3.0 ml of toluene were added, and it reacted by heating and stirring at 70 degreeC. After confirming the consumption of the first monomer by ¹ H NMR measurement, 40 mol equivalents of HEA (relative to the RAFT initiator) were added as the second monomer. After confirming that the unreacted monomer was consumed by ¹ H NMR measurement, 30 mol equivalent of StA (relative to RAFT initiator) was added as a third monomer. After confirming that unreacted monomers were consumed by ¹ H NMR measurement, block copolymer (13) was obtained by re-precipitation in acetone. The reaction proceeded quantitatively.

<Example 14> StA/diA

Example 11, except that 100 mol equivalent of StA as the first monomer and 1 mol equivalent of 1,6-bisacryloylhexane (diA) as the second monomer were used relative to 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate. The reaction was performed in the same manner as above to obtain a block copolymer (14).

<Example 15> C18URA/diA

Example 11, except that 100 mol equivalent of C18URA as the first monomer and 1 mol equivalent of 1,6-bisacryloylhexane (diA) as the second monomer were used relative to 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate. The reaction was performed in the same manner as above to obtain a block copolymer (15).

<Example 16> Emulsion polymerization StA/tBuA

In a nitrogen-purged reaction vessel, 27 mg of 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid, 4,4'-azobis(4-cyanovaleric acid) and StA as the first monomer were added as a RAFT initiator 0.1 mol equivalent and 32 mol equivalent, respectively, of polyethylene glycol monooleyl ether with respect to StA, 2.5% by weight and 3.0 ml of pure water were added, and an emulsified solution was prepared by applying ultrasonic waves, followed by heating and stirring at 70 ° C to react. did. After confirming the consumption of the first monomer by ¹ H NMR measurement, 18 mol equivalents of tBuA (relative to the RAFT initiator) were added as the second monomer. After confirming that the unreacted monomer was consumed by ¹ H NMR measurement, a block copolymer (16) was obtained by re-precipitation in acetone. The reaction proceeded quantitatively. The weight average molecular weight (Mw) of the block copolymer (16) was 14300, and the molecular weight distribution (Mw/Mn) was 1.15.

<Example 17> Emulsion polymerization StA/HEA

RAFT initiator 2-[(dodecylsulfanylthiocarbonyl)sulfanyl] propanoic acid 1 mol equivalent, 50 mol equivalent of StA as the first monomer, 5 mol equivalent of HEA as the second monomer, except that the reaction was the same as in Example 16 was carried out to obtain a block copolymer (17). The weight average molecular weight (Mw) of the block copolymer (17) was 14800, and the molecular weight distribution (Mw/Mn) was 1.17.

Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), copolymer composition, melting point, static and dynamic contact angle, water repellency test, strong water repellency of Examples 1 to 15 and Comparative Examples 1 to 6 The test results are shown in Table 1.

<Example 18> StA/HEA

A block copolymer (18 ) was obtained.

<Example 19> StA/(HBA/HBAGE)

Based on 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate, 80 mol equivalent of StA as the first monomer, 10 mol equivalent of hydroxybutyl acrylate (HBA) and 10 mol of hydroxybutyl acrylate glycidyl ether (HBAGE) as the second monomer A block copolymer (19) was obtained in the same manner as in Example 11, except that two types of monomers in equivalent amounts were added simultaneously. In the water repellency test of the block copolymer (19), the fabric after application and washing 20 times also scored 95 points (PET) and 95 points (Ny), and the water repellency performance was maintained even after washing.

<Comparative Example 7> StA/HEA

With respect to 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate, 80 mol equivalent of StA as the first monomer and 20 mol equivalent of HEA as the second monomer were used, except that the first and second monomers were added to the reaction vessel at the same time was reacted in the same manner as in Example 11 to obtain a random copolymer (7).

<Comparative Example 8> StA/GMA/HEA

4.0 ml of toluene, 18.3 mg of AIBN, and 2.2 g of StA, 0.39 g of HEA, and 0.16 g of glycidyl methacrylate (GMA) were added as monomers to a nitrogen-purged reaction vessel, followed by heating and stirring at 65°C to carry out a reaction. . After confirming that unreacted monomers were consumed by ¹ H NMR measurement, random copolymer (8) was obtained by re-precipitation in acetone. The reaction proceeded quantitatively.

<Example 20> C18 AmEA/HEA

40 mol equivalent of CH ₂ =CHCO ₂ -CH ₂ CH ₂ -NH-C(=O)-C ₁₇ H ₃₅ (C 18AmEA) as the first monomer relative to 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate, second A block copolymer (20) was obtained in the same manner as in Example 11, except that 60 mol equivalent of HEA was used as the monomer.

<Example 21> C18 AmEA/HEA

A block copolymer (21 ) was obtained.

<Example 22> C18 AmEA/HEA

A block copolymer (22 ) was obtained.

<Example 23> C18 AmEA/HEA

Block copolymer (23) got

<Example 24> C18AmEA/(StA/HEA)

Example, except that two monomers were simultaneously added to 30 mol equivalents of C18AmEA as the first monomer, 40 mol equivalents of StA and 30 mol equivalents of HEA as the second monomer, relative to 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate. The reaction was performed in the same manner as in 11 to obtain a block copolymer (24).

<Example 25> C18 AmEA/(GMA/HEA)

Example, except that 70 mol equivalents of C18AmEA as the first monomer and 6 mol equivalents of GMA and 24 mol equivalents of HEA as the second monomer were added simultaneously to 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate. The reaction was performed in the same manner as in 11 to obtain a block copolymer (25).

<Example 26> C18AmEA/tBuA

Block copolymer (26) got

<Example 27> C18AmEA/tBuA

Block copolymer (27) got

<Example 28> C18 AmEA/AA

With respect to 1 unit of tBuA of the block copolymer (26), a deprotection reaction was performed by reacting with 5 equivalents of trifluoroacetic acid, and the block copolymer (28) was obtained by re-precipitating in acetone.

<Example 29> C18AmEA/StA

A block copolymer ( 29) was obtained.

<Example 30> C18AmEA/StA

A block copolymer ( 30) was obtained.

<Comparative Example 9> C18 AmEA/HEA

A block copolymer (9 ) was obtained.

<Comparative Example 10> C18AmEA/HEA

A block copolymer (10 ) was obtained.

<Comparative Example 11> C18AmEA/HEA

With respect to 1 mol equivalent of ethyl 2-bromoisobutyrate as an initiator, 46 mol equivalent of C18AmEA as the first monomer and 54 mol equivalent of HEA as the second monomer were used, except that the first and second monomers were added to the reaction vessel at the same time. , The reaction was performed in the same manner as in Example 2 to obtain a random copolymer (11).

<Comparative Example 12> C18AmEA/HEA

A random copolymer (12) was obtained by reacting in the same manner as in Comparative Example 8, except that 50 mol equivalents of C18 AmEA and 50 mol equivalents of HEA were used as monomers with respect to 1 mol equivalent of AIBN as an initiator. The solubility of the obtained polymer in chloroform or toluene was low, and it was difficult to prepare a uniform coating film for evaluation of the contact angle or cloth.

<Comparative Example 13> C18 AmEA/HEA

A random copolymer (13) was obtained by reacting in the same manner as in Comparative Example 8, except that 70 mol equivalents of C18 AmEA and 30 mol equivalents of HEA were used as monomers with respect to 1 mol equivalent of AIBN as an initiator. The solubility of the obtained polymer in chloroform or toluene was low, and it was difficult to prepare a uniform coating film for evaluation of the contact angle or cloth.

<Comparative Example 14> C18AmEA/HEA

Random copolymer (14) was obtained by reacting in the same manner as in Comparative Example 8, except that 80 mol equivalents of C18AmEA and 20 mol equivalents of HEA were used as monomers with respect to 1 mol equivalent of AIBN as an initiator. The solubility of the obtained polymer in chloroform or toluene was low, and it was difficult to prepare a uniform coating film for evaluation of the contact angle or cloth.

<Comparative Example 15> StA/GMA/HEA

Random copolymer (15) was obtained by reacting in the same manner as in Comparative Example 8, except that 60 mol equivalent of StA, 10 mol equivalent of GMA, and 30 mol equivalent of HEA were used as monomers with respect to 1 mol equivalent of AIBN as an initiator.

<Comparative Example 16> C18 AmEA/GMA/HEA

Based on 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate, 60 mol equivalent of C18AmEA as the first monomer, 10 equivalent of GMA as the second monomer, and 30 mol equivalent of HEA as the third monomer were used, and the first monomer, the second monomer and the second monomer were used. A random copolymer (16) was obtained in the same manner as in Example 11 except that the three monomers were added to the reaction vessel at the same time.

<Comparative Example 17> C18AmEA/tBuA

With respect to 1 mol equivalent of ethyl 2-bromoisobutyrate as an initiator, 53 mol equivalent of C18AmEA as the first monomer and 47 mol equivalent of tBuA as the second monomer were used, except that the first and second monomers were added to the reaction vessel at the same time , The reaction was performed in the same manner as in Example 2 to obtain a random copolymer (17).

<Comparative Example 18> C18 AmEA/AA

A deprotection reaction was performed by reacting 1 unit of tBuA of the random copolymer (17) with 5 equivalents of trifluoroacetic acid, followed by reprecipitation in acetone to obtain a random copolymer (18).

<Comparative Example 19> C18AmEA/StA

With respect to 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate, 30 mol equivalent of C18 AmEA as the first monomer and 70 mol equivalent of HEA as the second monomer were used, except that the first and second monomers were added to the reaction vessel at the same time. reacted in the same manner as in Example 11 to obtain a random copolymer (19).

<Example 31> C18AmEA/HEA/diA

Based on 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate, 100 mol equivalent of C18AmEA as the first monomer, 1 mol equivalent of HEA as the second monomer, CH ₂ =CHCO ₂ -C ₆ H ₁₂ -CO ₂ CH= as the third monomer A block copolymer (31) was obtained in the same manner as in Example 11, except that 1 mol equivalent of CH ₂ (diA) was used and the third monomer was added after confirming the consumption of the second monomer.

<Example 32> C18AmEA/tBuA/diA

100 mol equivalent of C18AmEA as the first monomer, 1 mol equivalent of tBuA as the second monomer, and 1 mol equivalent of diA as the third monomer, relative to 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate, After confirming the consumption of the second monomer A block copolymer (32) was obtained in the same manner as in Example 11 except that the third monomer was added.

<Example 33> C18AmEA/AA/diA

With respect to 1 unit of tBuA of the block copolymer (32), a deprotection reaction was performed by reacting with 5 equivalents of trifluoroacetic acid, and the block copolymer (33) was obtained by re-precipitating in acetone.

<Example 34> C18 AmEA/HEA/diA

With respect to 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate, 38 mol equivalent of C18AmEA as the first monomer, 51 mol equivalent of HEA as the second monomer, and 11 mol equivalent of StA as the third monomer, After confirming the consumption of the second monomer A block copolymer (34) was obtained in the same manner as in Example 11 except that the third monomer was added.

<Example 35> C18 AmEA/diA

A block copolymer ( 35) was obtained.

<Example 36> C18 AmEA/HEA

RAFT initiator 2-[(dodecylsulfanylthiocarbonyl)sulfanyl]propanoic acid 1 mol equivalent, as in Example 16, except that 50 mol equivalent of C AmEA as the first monomer and 5 mol equivalent of HEA as the second monomer were used. The reaction was performed to obtain a block copolymer (36).

<Example 37> (C18 AmEA/StA)/HEA

With respect to 1 mol equivalent of RAFT initiator cyanomethyldodecyltrithiocarbonate, 40 mol equivalents of C18AmEA and 4040 mol equivalents of StA were used as the first monomers, and 20 mol equivalents of HEA were used as the second monomer. The reaction was carried out in the same manner as in Example 11, A block copolymer (37) was obtained. In the water repellency test of the block copolymer (37), the fabric after application and washing 20 times also scored 95 points (PET) and 95+ points (Ny), and the water repellency performance was maintained even after washing.

Number average molecular weight (Mn), weight average molecular weight (Mw), molecular weight distribution (Mw/Mn), copolymer composition, melting point, static and dynamic contact angle, water repellency test, strong water repellency of Examples 16 to 37 and Comparative Examples 7 to 19 The results of the test are shown in Table 2.

The surface treatment agent of the present disclosure can be used as a water and oil repellent agent or an antifouling agent. The surface treatment agent can be suitably used for substrates such as textile products and masonry, and imparts excellent water and oil repellency to the substrates.

Claims (20)

A non-fluorine block copolymer having at least one block segment (A),
The block segment (A) has a repeating unit formed of one or two or more acrylic monomers having a long-chain hydrocarbon group of 12 to 40 carbon atoms,
An acrylic monomer having a long-chain hydrocarbon group,
(a2) formula:
CH ₂ =C(-R ³² )-C(=O)-Y ³¹ -Z ³¹ (-Y ³² -R ³¹ ) _n
[Wherein, R ³¹ is a hydrocarbon group having 12 to 40 carbon atoms,
R ³² is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom;
Y ³¹ is -O- or -NH-;
Y ³² is a group composed of at least one selected from -C ₆ H ₄ -, -O-, -C(=O)-, -S(=O) ₂ -, or -NH-;
Z ³¹ is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms;
n is 1 or 2.]
is a compound represented by
A non-fluorine block copolymer wherein the molar ratio (molar ratio of repeating units) of the block segment (A) is 30 mol% or more with respect to the repeating units of the copolymer. The method of claim 1, wherein the non-fluorine block copolymer has a segment (B) different from the block segment (A), and segment (B) is
(B1) a block segment having a repeating unit formed of an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms different from the segment (A);
(B2) a block segment having a repeating unit formed of an acrylic monomer having no long-chain hydrocarbon group;
(B3) random segments formed of at least two kinds of acrylic monomers
A non-fluorine block copolymer having at least one of The method according to claim 1, in the acrylic monomer (a2),
R ³² is a hydrogen atom, a methyl group or a chlorine atom;
Y ³² is
-O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S (=O) ₂ -, -S(=O) ₂ -NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH -, -OC ₆ H ₄ -, -NH-C ₆ H ₄ -, -O-(CH ₂ ) _m -O-, -NH-(CH ₂ ) _m -NH-, -O-(CH ₂ ) _m -NH-, -NH-(CH ₂ ) _m -O-, -O-(CH ₂ ) _m -OC(=O)-, -O-(CH ₂ ) _m -C(=O)-O-, -NH-(CH ₂ ) _m -OC(=O)-, -NH-(CH ₂ ) _m -C(=O)-O-, -O-(CH ₂ ) _m -OC(=O)-NH -, -O-(CH ₂ ) _m -NH-C(=O)-O-, -O-(CH ₂ ) _m -C(=O)-NH-, -O-(CH ₂ ) _m -NH -C(=O)-, -O-(CH ₂ ) _m -NH-C(=O)-NH-, -O-(CH ₂ ) _m -OC ₆ H ₄ -, -NH-(CH ₂ ) _m -OC(=O)-NH-, -NH-(CH ₂ ) _m -NH-C(=O)-O-, -NH-(CH ₂ ) _m -C(=O)-NH-, - NH-(CH ₂ ) _m -NH-C(=O)-, -NH-(CH ₂ ) _m -NH-C(=O)-NH-, -NH-(CH ₂ ) _m -OC ₆ H ₄ - or -NH-(CH ₂ ) _m -NH-C ₆ H ₄ -
[In the formula, m is an integer of 1 to 5.]
ego,
Z ³¹ is -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, a branched structure -CH ₂ CH= having a branched structure, -CH ₂ (CH-)CH ₂ - having a branched structure, -CH ₂ CH ₂ CH= having a branched structure, -CH ₂ CH ₂ CH ₂ CH ₂ CH= having a branched structure , -CH ₂ CH ₂ (CH-)CH ₂ - having a branched structure, or -CH ₂ CH ₂ CH ₂ CH= having a branched structure. The acrylic monomer having a long-chain hydrocarbon group of the block segment (B1) according to claim 2, wherein the long-chain hydrocarbon group is a straight-chain or branched alkyl group having 10 to 40 carbon atoms, and the acrylic monomer having no long-chain hydrocarbon group has 1 to 6 carbon atoms. An acrylic monomer having a short-chain hydrocarbon group, an acrylic monomer having a dimethylsiloxane moiety in the side chain, an acrylic monomer having a hydrophilic group, an acrylic monomer having a cyclic hydrocarbon group, an acrylic monomer having a crosslinked moiety, or a halogenated olefin, and the hydrophilic group is an OH group or an NH ₂ group. , a COOH group, a sulfone group or a phosphoric acid group, an alkali metal or alkaline earth metal base of a carboxylic acid, a non-fluorine block copolymer. The method according to claim 4, wherein the acrylic monomer having a short chain hydrocarbon group having 1 to 6 carbon atoms has the formula:
CH ₂ =C(-R ⁵² )-C(=O)-Y ⁵¹ -R ⁵¹
[Wherein, R ⁵¹ is a hydrocarbon group having 1 to 6 carbon atoms (which may contain oxygen atoms);
R ⁵² is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom;
Y ⁵¹ is -O- or -NH-.]
It is a compound represented by
An acrylic monomer having a hydrophilic group has the formula:
CH ₂ =C(-R ⁶² )-C(=O)-Y ⁶¹ -R ⁶¹ -(-Y ⁶² ) _q
[Wherein, R ⁶¹ is a hydrocarbon group having 1 to 6 carbon atoms or a single bond;
R ⁶² is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom;
Y ⁶¹ is -O- or -NH-;
Y ⁶² is a hydrophilic group;
q is a number from 1 to 3.]
A non-fluorine block copolymer, which is a compound represented by The fluorine-free block copolymer according to claim 1 or 2, wherein the molar ratio of the block segments (A) (molar ratio of the repeating units) is 35 to 99 mol% with respect to the repeating units of the copolymer. A first-stage polymerization step of polymerizing either an acrylic monomer having a long-chain hydrocarbon group or an acrylic monomer not having a long-chain hydrocarbon group, and then a step of polymerizing the other of the acrylic monomer having a long-chain hydrocarbon group or not having a long-chain hydrocarbon group. The method for producing a fluorine-free block copolymer according to claim 1 or 2, wherein the fluorine-free block copolymer is produced by a second stage polymerization step. (1) the fluorine-free block copolymer according to claim 1 or 2, and
(2) A liquid medium, which is an organic solvent, or a liquid medium that is water, an organic solvent, or a mixture of water and an organic solvent.
A surface treatment agent comprising a. The surface treatment agent according to claim 8, wherein the surface treatment agent is a water repellent agent. The substrate to which the non-fluorine block copolymer in the surface treatment agent according to claim 8 is adhered. A method for producing a treated substrate comprising applying the surface treatment agent according to claim 8 to the substrate. (1) a non-fluorine block copolymer and
(2) A liquid medium, which is an organic solvent, or a liquid medium that is water, an organic solvent, or a mixture of water and an organic solvent.
A surface treatment agent comprising
The non-fluorine block copolymer is a non-fluorine block copolymer having at least one block segment (A) and another segment (B);
The block segment (A) has a repeating unit formed of one or two or more acrylic monomers having a long-chain hydrocarbon group of 7 to 40 or 10 to 40 carbon atoms,
An acrylic monomer having a long-chain hydrocarbon group,
(a1) formula:
CH ₂ =C(-R ²² )-C(=O)-Y ²¹ -R ²¹
[Wherein, R ²¹ is a hydrocarbon group having 10 to 40 carbon atoms,
R ²² is a hydrogen atom or a halogen atom other than a fluorine atom;
Y ²¹ is -O- or -NH-.]
A compound represented by , and
(a2) formula:
CH ₂ =C(-R ³² )-C(=O)-Y ³¹ -Z ³¹ (-Y ³² -R ³¹ ) _n
[Wherein, R ³¹ is a hydrocarbon group having 7 to 40 carbon atoms,
R ³² is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom;
Y ³¹ is -O- or -NH-;
Y ³² is a group composed of at least one selected from -C ₆ H ₄ -, -O-, -C(=O)-, -S(=O) ₂ -, or -NH-;
Z ³¹ is a divalent or trivalent hydrocarbon group having 1 to 5 carbon atoms;
n is 1 or 2.]
compound represented by
At least one monomer selected from the group consisting of
Another segment (B) is
(B1) a block segment having a repeating unit formed of an acrylic monomer having a long-chain hydrocarbon group having 7 to 40 carbon atoms different from the segment (A);
(B2) a block segment having a repeating unit formed of an acrylic monomer having no long-chain hydrocarbon group, and
(B3) random segments formed of at least two kinds of acrylic monomers
At least one segment selected from the group consisting of
The acrylic monomer having no long-chain hydrocarbon group in the block segment (B2) includes an acrylic monomer having a short-chain hydrocarbon group having 1 to 6 carbon atoms, an acrylic monomer having a hydrophilic group, an acrylic monomer having a cyclic hydrocarbon group, a halogenated olefin, and a dimethylsiloxane moiety as a side chain. at least one member selected from the group consisting of an acrylic monomer, a divinyl compound, and a silicon-containing compound,
At least two types of acrylic monomers in the random segment (B3) include an acrylic monomer having a long-chain hydrocarbon group of 7 to 40 carbon atoms, an acrylic monomer having a short-chain hydrocarbon group of 1 to 6 carbon atoms, an acrylic monomer having a hydrophilic group, and a cyclic hydrocarbon group. at least two selected from the group consisting of an acrylic monomer, a halogenated olefin, a monomer having a dimethylsiloxane group, a divinyl compound, and a silicon-containing compound;
An acrylic monomer having a short-chain hydrocarbon group having 1 to 6 carbon atoms has the formula:
CH ₂ =C(-R ⁵² )-C(=O)-Y ⁵¹ -R ⁵¹
[Wherein, R ⁵¹ is a hydrocarbon group having 1 to 6 carbon atoms (may contain an oxygen atom) (except for a methyl group);
R ⁵² is a hydrogen atom or a halogen atom other than a fluorine atom;
Y ⁵¹ is -O- or -NH-.]
It is a compound represented by
The surface treatment agent whose molar ratio (molar ratio of repeating units) of the block segment (A) is 30 mol% or more with respect to the repeating unit of a copolymer. The method of claim 12, in the acrylic monomer (a1),
R ²² is a hydrogen atom or a chlorine atom;
In the acrylic monomer (a2),
R ³² is a hydrogen atom, a methyl group or a chlorine atom;
Y ³² is
-O-, -NH-, -OC(=O)-, -C(=O)-O-, -C(=O)-NH-, -NH-C(=O)-, -NH-S (=O) ₂ -, -S(=O) ₂ -NH-, -OC(=O)-NH-, -NH-C(=O)-O-, -NH-C(=O)-NH -, -OC ₆ H ₄ -, -NH-C ₆ H ₄ -, -O-(CH ₂ ) _m -O-, -NH-(CH ₂ ) _m -NH-, -O-(CH ₂ ) _m -NH-, -NH-(CH ₂ ) _m -O-, -O-(CH ₂ ) _m -OC(=O)-, -O-(CH ₂ ) _m -C(=O)-O-, -NH-(CH ₂ ) _m -OC(=O)-, -NH-(CH ₂ ) _m -C(=O)-O-, -O-(CH ₂ ) _m -OC(=O)-NH -, -O-(CH ₂ ) _m -NH-C(=O)-O-, -O-(CH ₂ ) _m -C(=O)-NH-, -O-(CH ₂ ) _m -NH -C(=O)-, -O-(CH ₂ ) _m -NH-C(=O)-NH-, -O-(CH ₂ ) _m -OC ₆ H ₄ -, -NH-(CH ₂ ) _m -OC(=O)-NH-, -NH-(CH ₂ ) _m -NH-C(=O)-O-, -NH-(CH ₂ ) _m -C(=O)-NH-, - NH-(CH ₂ ) _m -NH-C(=O)-, -NH-(CH ₂ ) _m -NH-C(=O)-NH-, -NH-(CH ₂ ) _m -OC ₆ H ₄ - or -NH-(CH ₂ ) _m -NH-C ₆ H ₄ -
[In the formula, m is an integer of 1 to 5.]
ego,
Z ³¹ is -CH ₂ -, -CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ -, -CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ -, a branched structure -CH ₂ CH= having a branched structure, -CH ₂ (CH-)CH ₂ - having a branched structure, -CH ₂ CH ₂ CH= having a branched structure, -CH ₂ CH ₂ CH ₂ CH ₂ CH= having a branched structure , -CH ₂ CH ₂ (CH-)CH ₂ - having a branched structure, or -CH ₂ CH ₂ CH ₂ CH= having a branched structure. The method according to claim 12 or 13, in the acrylic monomer having a long-chain hydrocarbon group, the long-chain hydrocarbon group is a straight-chain or branched alkyl group having 10 to 40 carbon atoms,
In the acrylic monomer having a hydrophilic group, the hydrophilic group is an OH group, an NH ₂ group, a COOH group, a sulfone group or a phosphoric acid group, or an alkali metal or alkaline earth metal base of a carboxylic acid. The acrylic monomer having a hydrophilic group according to claim 12 or 13 has the formula:
CH ₂ =C(-R ⁶² )-C(=O)-Y ⁶¹ -R ⁶¹ -(-Y ⁶² ) _q
[Wherein, R ⁶¹ is a hydrocarbon group having 1 to 6 carbon atoms or a single bond;
R ⁶² is a hydrogen atom, a monovalent organic group or a halogen atom other than a fluorine atom;
Y ⁶¹ is -O- or -NH-;
Y ⁶² is a hydrophilic group;
q is a number from 1 to 3.]
A surface treatment agent that is a compound represented by The surface treatment agent according to claim 12 or 13, wherein the block segment (A) has a molar ratio (molar ratio of repeating units) of 35 mol% or more relative to the repeating units of the copolymer. A first-stage polymerization step of polymerizing either an acrylic monomer having a long-chain hydrocarbon group or an acrylic monomer not having a long-chain hydrocarbon group, and then a step of polymerizing the other of the acrylic monomer having a long-chain hydrocarbon group or not having a long-chain hydrocarbon group. The manufacturing method of the surface treatment agent of Claim 12 or 13 which manufactures a fluorine-free block copolymer by the 2nd stage polymerization process. The surface treatment agent according to claim 12 or 13, wherein the surface treatment agent is a water repellent agent. The base material to which the non-fluorine block copolymer in the surface treatment agent according to claim 12 or 13 has adhered. A method for producing a treated substrate comprising applying the surface treatment agent according to claim 12 or 13 to the substrate.